CN107428611A - Dispersant for hydraulic composition composition - Google Patents

Dispersant for hydraulic composition composition Download PDF

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Publication number
CN107428611A
CN107428611A CN201680018291.4A CN201680018291A CN107428611A CN 107428611 A CN107428611 A CN 107428611A CN 201680018291 A CN201680018291 A CN 201680018291A CN 107428611 A CN107428611 A CN 107428611A
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compound
hydraulic
group
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CN107428611B (en
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田中骏也
下田政朗
齐田和哉
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Kao Corp
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Kao Corp
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/20—Sulfonated aromatic compounds
    • C04B24/22—Condensation or polymerisation products thereof
    • C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/122—Hydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/20—Sulfonated aromatic compounds
    • C04B24/22—Condensation or polymerisation products thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2611—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Lubricants (AREA)

Abstract

The present invention relates to a kind of dispersant for hydraulic composition composition, it contains：(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit, (B) contain with selected from carboxylic acid group, phosphate, the group for being changed into by hydrolysis carboxylic acid group and by hydrolysis being changed into the monomeric unit of group in the group of phosphate and monomeric unit, weight average molecular weight 1 with alkylene oxide group, more than 000 and 1,000, less than 000 polymer, and the specific compound represented by (C) formula (C1)~(C4).

Description

Dispersant for hydraulic composition composition
Technical field
The present invention relates to dispersant for hydraulic composition composition and hydraulic-composition.
Background technology
The dispersant of hydraulic-composition is in order to by disperseing cement granules, so as to get required slump institute is necessary Unit discharge reduction, and improve workability of hydraulic-composition etc. and use chemistry mix agent.As dispersant, past The naphthalene such as known naphthalene sulfonic acid-formaldehyde condensation product system dispersant, carboxylic acid are with having the polycarboxylic acids such as the copolymer of monomer of alkylene glycol chain It is the melamine system such as dispersant, melamine sulfonic formaldehyde condensation compound dispersant etc..
Compared with polycarboxylic-acid dispersant, naphthalene system dispersant has following feature：For material, the change of temperature, flowing The change of the effect of sex expression is less, and gained hydraulic-composition is sticky relatively low in addition, in the system of hydraulic-composition Easily used when making.
On the other hand, compared with naphthalene system dispersant, polycarboxylic-acid dispersant has following feature：Even for relatively low Water/cement than hydraulic-composition can also show good dispersiveness.But as Japanese Unexamined Patent Publication 2003-321264 Technical problem in number publication, Japanese Unexamined Patent Publication 2007-210877 publications, Japanese Unexamined Patent Publication 2011-207669 publications, polycarboxylic acids It is that the performance of the effect of dispersant has temperature dependency, at a high temperature of summer etc. and in a low temperature of winter etc., mobility, material The effect of material separation repellence etc changes.
Japanese Unexamined Patent Publication 2003-321264 publications are disclosed containing poly carboxylic acid series water reducer, cement and specific carboxylic acid list The hydraulic-composition of the metal salt of body.
Japanese Unexamined Patent Publication 2007-210877 publications disclose containing specific polycarboxylic acid polymer and have specific phosphorus The dispersant for hydraulic composition of the polymer of acidic group.
Japanese Unexamined Patent Publication 2011-207669 publications are disclosed comprising hydraulicity composition, inanimate matter micropowder and specific The hydraulic-composition of modified polycarboxylic acid system flowing agent.
If it is believed that naphthalene system dispersant and polycarboxylic-acid dispersant are used in combination, show for relatively low water/ Cement than hydraulic-composition good dispersion while, can solve the technical problem of temperature dependency, but actual It is upper as described in Japanese Unexamined Patent Publication 2006-169078 publications, Japanese Unexamined Patent Publication 2006-168305 publications, if by naphthalene system Dispersant is used in combination with polycarboxylic-acid dispersant, then the mobility of hydraulic-composition reduces, and can not obtain being resistant to practicality The dispersant of level.
Japanese Unexamined Patent Publication 2006-169078 publications disclose the polycarboxylic acids chemical combination for having more than 3 carboxyls containing every 1 molecule Thing, naphthalene sulfonic acids based water reducer and the solubility in water are the cement water reducer of the calcium salt of solubility acid more than 5 (25 DEG C).
Japanese Unexamined Patent Publication 2006-168305 publications, which disclose, to have the Polycarboxylated of more than 3 carboxyls containing every 1 molecule Compound, its calcium salt are addition after hydraulic-composition and the water mixing of soluble sour alkali metal salt and cement in water The adding method of the cement water reducer of sulfonic acid based water reducer.
The content of the invention
The present invention, which provides, can maintain to assign the mobility of hydraulic-composition effect, and the mobility assigns the temperature of effect It is small to spend dependence, the dispersant for hydraulic composition composition of the good initial strength of hydraulic-composition can be assigned in addition.
The present invention relates to：
A kind of dispersant for hydraulic composition composition, it contains：
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change Monomeric unit for the group in the group of phosphate and monomeric unit, the weight average molecular weight 1,000 with alkylene oxide group Above and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by.
【Chemical formula 1】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
Moreover, it relates to：
A kind of hydraulic-composition, it contains：
Hydraulic powder,
Water,
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by.
【Chemical formula 2】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
Moreover, it relates to：
A kind of inorganic particle dispersant composition, it contains：
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by.
【Chemical formula 3】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
Hereinafter, using (A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit to be illustrated as (A) composition.
Carboxylic acid group, phosphate are selected from, the group of carboxylic acid group is changed into by hydrolysis and passed through in addition, (B) is contained and had Hydrolysis is changed into the group monomer unit of the group of phosphate, monomeric unit, weight average molecular weight 1 with having alkylene oxide group, More than 000 and less than 1,000,000 polymer illustrates as (B) composition.
In addition, using the compound represented by the formula (C1) as compound (C1), the formula (C2) is represented Compound as compound (C2), using the compound represented by the formula (C3) as compound (C3), by the formula (C4) compound represented by illustrates as compound (C4).
Further, compound (C1), compound (C2), compound (C3) and compound (C4) are referred to as (C) composition Illustrate.
According to the present invention, it is possible to provide be able to maintain that and effect and mobility tax are assigned to the mobility of hydraulic-composition Give that the temperature dependency of effect is small, can assign the hydraulic-composition of the good initial strength of hydraulic-composition in addition with scattered Agent composition.
Embodiment
(dispersant for hydraulic composition composition)
(A) composition can be used as naphthalene system dispersant to play function.In addition, (B) composition can be used as polycarboxylic-acid dispersant to play Function.(B) composition is being changed into the group of carboxylic acid group with phosphate, by hydrolysis or is being changed into the base of phosphate by hydrolysis Also there is identical function in the case of group.If thickening and dispersed occurring naphthalene system dispersant and polycarboxylic-acid dispersant and with if Reduce.It is believed that because the poly- alkylene oxide group (AO chains) of the naphthalene nucleus of naphthalene system dispersant and polycarboxylic-acid dispersant is formed Close, therefore dispersant occurs molecular weight from the form of expression and thickens, associates, be thus adsorbed to cement it is hindered and Dispersiveness reduces.If it is believed that further and using (C) composition, (C) composition shows interaction with naphthalene nucleus so that naphthalene nucleus Association with AO chains is eliminated or weakened, and thickening is suppressed.And, it is believed that naphthalene system dispersant and polycarboxylic-acid dispersant Cement is adsorbed to different suction types respectively and plays dispersiveness, as a result can obtain naphthalene system dispersant and polycarboxylic-acid The independent unavailable performance of dispersant.It is believed that (C) composition is dredged to be solvable in naphthalene system aqueous dispersant with certain The compound of water-based functional group, the interaction of (C) composition and naphthalene nucleus are based on hydrophily and hydrophobic balance.
＜ (A) compositions ＞
(A) composition is with the high-molecular compound for wrapping naphthalene-ring containing monomeric unit.(A) composition can be used as example, containing The dispersant for having the hydraulic-composition of the hydraulic powders such as cement, gypsum uses.
As (A) composition, naphthalene sulfonic acid-formaldehyde condensation product or its salt are preferably enumerated.Naphthalene sulfonic acid-formaldehyde condensation product or its salt are Naphthalene sulfonic acids and the condensation product of formaldehyde or its salt.As long as not damaging energy, naphthalene sulfonic acid-formaldehyde condensation product can also with such as methyl naphthalene, Ethylnaphthalene, dibutyl naphthalene, hydroxyl naphthalene, naphthalene-carboxylic acid, anthracene, phenol, cresols, creasote, tar, melamine, urea, p-aminobenzene sulfonic acid And/or their derivative or the like as monomer, cocondensation can be carried out with the aromatic compound of naphthalene sulfonic acids cocondensation.
Naphthalene sulfonic acid-formaldehyde condensation product or its salt can be used for example, Mighty150, DEMOL N, DEMOL RN, DEMOL MS, DEMOL SN-B, DEMOL SS-L (being Kao Corp's system), Celluflow 120, Ravelin FD-40, Commercially available product as Ravelin FM-45 (being first Industrial Co., Ltd's system) etc..
From the viewpoint of the mobility of hydraulic-composition improves, the Weight-average molecular of naphthalene sulfonic acid-formaldehyde condensation product or its salt Amount is preferably less than 200,000, is more preferably less than 100,000, is more preferably less than 80,000, is still more preferably Less than 50,000, still more preferably it is less than 30,000.Also, the viewpoint improved from the mobility of hydraulic-composition goes out The weight average molecular weight of hair, naphthalene sulfonic acid-formaldehyde condensation product or its salt is preferably 1, more than 000, is more preferably 3, more than 000, further Preferably more than 4,000, still more preferably it is more than 5,000.Naphthalene sulfonic acid-formaldehyde condensation product can be acid state either Corrective.
The molecular weight of naphthalene sulfonic acid-formaldehyde condensation product or its salt can be measured with gel permeation chromatography under the following conditions.
[GPC conditions]
Chromatographic column：G4000SWXL+G2000SWXL (eastern Cao)
Eluent：30mM CH3COONa/CH3CN=6/4
Flow：0.7ml/min
Detection wavelength：UV280nm
Sample size：0.2mg/ml
Standard substance：Western tail industrial (strain) kayexalate conversion (monodisperse polystyrene sodium sulfonate processed：Molecule Amount：206、1,800、4,000、8,000、18,000、35,000、88,000、780,000)
Detector：TOSOH Co., Ltd UV-8020
The manufacture method of naphthalene sulfonic acid-formaldehyde condensation product or its salt can be enumerated for example, by the way that naphthalene sulfonic acids and formaldehyde are condensed React and obtain the method for condensation product.The neutralization of above-mentioned condensation product can be carried out.Alternatively, it is also possible to remove by-product by neutralizing Water-insoluble.Specifically, in order to obtain naphthalene sulfonic acids, relative to 1 mole of naphthalene, using 1.2~1.4 moles of sulfuric acid, and it is allowed to 2~5 hours are reacted at 150~165 DEG C so as to obtain sulfonated bodies.Then, relative to 1 mole of the sulfonated bodies, so that formaldehyde is 0.95~0.99 mole of mode lasts 3~6 hours at 85~95 DEG C and formalin is added dropwise, after dropwise addition at 95~105 DEG C Carry out condensation reaction.In addition, the viewpoint from suppression metal erosion such as storage tank as caused by the aqueous acidity height of gained condensation product Set out, water and nertralizer can be added to gained condensation product, and neutralization step is carried out at 80~95 DEG C.Nertralizer preferably with respect to Naphthalene sulfonic acids and unreacted sulfuric acid add 1.0~1.1 moles times respectively.Furthermore it is possible to remove the water-insoluble as caused by neutralization, make Preferably enumerate for its method and separated using filtering.By these processes, it is water-soluble naphthalene sulfonic acid-formaldehyde condensation product can be obtained The aqueous solution of property salt.The aqueous solution can use directly as the aqueous solution of (A) composition.As needed can be further by the water Solution is dried, powdered so as to obtain the salt of powdered naphthalene sulfonic acid-formaldehyde condensation product, and can be as powder (A) composition of shape uses.Dry, powdered can be carried out by spray drying, roller drying, freeze-drying etc..
＜ (B) compositions ＞
(B) composition be containing with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and pass through water Solution is changed into the monomeric unit of the group in the group of phosphate, monomeric unit, weight average molecular weight with having alkylene oxide group More than 1,000 and less than 1,000,000 polymer.
Polymer is the compound obtained by addition polymerization, condensation polymerization.It is to make that there is unsaturation as addition polymerization The method of the monomer reaction of key, radical polymerization, ionic polymerization etc. can be enumerated.As condensation polymerization, can enumerate with aromatic series The formaldehyde condensation of compound is representative, addition condensation using aldehydes etc..
(B) carboxylic acid group of composition is-COOM0(M0Represent counter ion counterionsl gegenions.) represented by group.Carboxylic acid group is to be selected from carboxyl With the group of the carboxyl into salt.
In addition, the group for being changed into carboxylic acid group by hydrolysis as (B) composition, can enumerate carboxylic acid ester groups.Carboxylic acid ester groups With-COOR, (R represents alkyl, preferably carbon number more than 1 and less than 12 alkyl or hydroxy alkyl.) ester structure, and remain Pass through the structure that carboxylic acid group caused by hydrolysis is (B) composition.The group that carboxylic acid ester groups etc. is changed into carboxylic acid group by hydrolysis is tool There is the group for the precursor structures that can be described as carboxylic acid group., can be by carboxylic acid ester groups by the polymerization of the monomer with carboxylic acid ester groups Import in the polymer of (B) composition.
Preferably it is changed into the group of carboxylic acid group by hydrolysis in the viewpoint of initial strength.In addition, in flowing retentivity Preferably it is changed into the group of carboxylic acid group in viewpoint by hydrolysis.
In addition, the phosphate of (B) composition is-OPO (OM1)(OM2)(M1、M2It is identical or different, respectively represent contend with from Son.) represented by group.Phosphate is the group of the phosphate selected from phosphate and into salt.
Here, M0、M1、M2Hydrogen ion, alkali metal ion, alkaline-earth metal ion (1/2 atom), ammonium ion, amine can be enumerated Deng.
In addition, the group for being changed into phosphate by hydrolysis as (B) composition, can be enumerated phosphate-based.It is phosphate-based With the structure represented by following formula.
【Chemical formula 4】
(in formula, Ra、RbAlkyl, preferably carbon number more than 1 and less than 12 alkyl or hydroxy alkyl are represented respectively.)
The phosphate-based structure remained by phosphate caused by hydrolysis for (B) composition.It is phosphate-based etc. to pass through hydrolysis The group for being changed into phosphate is the group with the precursor structures that can be described as phosphate.By with phosphate-based monomer Polymerization, can by it is phosphate-based importing (B) composition polymer in.
Preferably it is changed into the group of phosphate by hydrolysis in the viewpoint of initial strength.In addition, in flowing retentivity Preferably it is changed into the group of phosphate in viewpoint by hydrolysis.
(B) composition can be containing with selected from carboxylic acid group, phosphate, carboxylic acid ester groups and it is phosphate-based in group list Body unit, with there is the monomeric unit of alkylene oxide group, weight average molecular weight more than 1,000 and less than 1,000,000 polymer.
(B) alkylene oxide group of composition can be enumerated for example, ethyleneoxy group, propylidene epoxide.They are preferably poly- ethylidene The product of addition polymerization occurs for epoxide, polytrimethylene epoxide etc., more than 2 moles of alkylene oxide group.
(B) composition is preferably selected from the polymer comprising the monomeric unit with carboxylic acid group and comprising with carboxylic acid group's Monomeric unit and with phosphate monomeric unit polymer in polymer.
As (B) composition, can enumerate for example, phosphate and/or carboxylic acid compound with unsaturated bond with containing Possesses the addition polymer of the compound of the monomeric unit of the alkylene oxide group of unsaturated bond, containing with selected from carboxylic acid group and phosphoric acid The monomeric unit of group in base is with having condensation product of the compound of the monomeric unit of alkylene oxide group and formaldehyde etc..
(B) weight average molecular weight of composition is 1, more than 000 1, less than 000,000, is carried from the mobility of hydraulic-composition From the viewpoint of height, weight average molecular weight is preferably 5, more than 000, more preferably 10, more than 000, more preferably 30,000 More than, preferably 500, less than 000, more preferably 150, less than 000, still more preferably be 100, less than 000.
Such as (B) composition, it can enumerate：
(1) alkoxy polyalkyleneglycol list (methyl) acrylate is with being selected from (methyl) acrylic acid, can have hydroxyl Carbon number more than 1 and less than 3 (methyl) acrylate and phosphate with unsaturated group in more than a kind be copolymerized Copolymer,
(2) ether compound of PAG and unsaturated alcohol and more than a kind in dicarboxylic acids and dicarboxylic anhydride The copolymer being copolymerized.
Here, (methyl) acrylate refers to acrylate or methacrylate, and (methyl) acrylic acid refers to acrylic acid Or methacrylic acid.
As the monomeric unit with carboxylic acid group, it can enumerate and come from selected from the unsaturated bond that can carry out addition polymerization Monocarboxylic acid and the monomeric unit with more than a kind of monomer in the dicarboxylic acids for the unsaturated bond that can carry out addition polymerization.For example, Can enumerate come from a kind in acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid with On monomer monomeric unit, preferably come from the monomer list of more than a kind of the monomer in methacrylic acid and acrylic acid Member.It can also be the monomeric unit using half esters such as the anhydride compounds such as maleic anhydride, maleic mono-esters as monomer.
As the monomeric unit with the group for being changed into carboxylic acid group by hydrolysis, it can enumerate and come from carboxylic acid ester groups The monomeric unit of monomer.For example, it is preferable to come from selected from 2- hydroxyethylmethacry,ates, methacrylate and ethylacrylic acid The monomeric unit of more than a kind of monomer in ester, more preferably come from the monomeric unit of 2- hydroxyethylmethacry,ates.
As the monomeric unit with the group selected from phosphate, can enumerate to come to be selected to have can carry out addition polymerization More than a kind in the phosphate cpd of unsaturated bond and phosphate cpd with the aromatic functional groups that can carry out condensation polymerization Monomer monomeric unit.Come from for example, can enumerate selected from di(2-ethylhexyl)phosphate ((2- hydroxyethyls) methacrylic acid) ester, di(2-ethylhexyl)phosphate ((2- hydroxyethyls) acrylic acid) ester, mono phosphoric acid ester (2- hydroxyethyls) methacrylate, mono phosphoric acid ester (2- hydroxyethyls) propylene More than a kind of list in acid esters, polyalkylene glycol mono (methyl) acrylate acid phosphoric acid ester and phenoxetol phosphate The monomeric unit of body, preferably come from selected from di(2-ethylhexyl)phosphate ((2- hydroxyethyls) methacrylic acid) ester, mono phosphoric acid ester (2- hydroxyethyls) The monomeric unit of more than a kind of monomer in methacrylate and phenoxetol phosphate.Alternatively, it is also possible to being these Central any more than a kind of alkali metal salt, alkali earth metal salt, ammonium salt, amine salt.
As the monomeric unit with the group for being changed into phosphate by hydrolysis, it can enumerate and come from phosphate-based The monomeric unit of monomer.For example, it is preferable to come from selected from dimethyl monohydroxy ethylmethyl acrylate phosphate, diethyl list hydroxyl More than a kind in base ethylmethyl acrylate phosphate, dihydroxy ethyl monohydroxy ethylmethyl acrylate phosphate The monomeric unit of monomer, more preferably come from the monomeric unit of dihydroxy ethyl monohydroxy ethylmethyl acrylate phosphate.
As the monomeric unit with alkylene oxide group, it can enumerate and come from unsaturated bond and Asia with addition polymerization can be carried out The monomeric unit of the compound of alkoxy.Come from for example, can enumerate selected from alkoxy polyalkyleneglycol list (methyl) acrylic acid The monomeric unit of more than a kind of monomer in the ether compound of ester and PAG and unsaturated alcohol.As with alkylene The monomeric unit of epoxide, specifically, it can enumerate and come from selected from methoxy poly (ethylene glycol), the poly- ethylidene polytrimethylene two of methoxyl group The poly- ethylidene polytrimethylene glycol of alcohol, ethyoxyl polyethylene glycol, ethyoxyl, propoxyl group polyethylene glycol, the poly- ethylidene of propoxyl group gather The carboxylate of the single end alkyl such as trimethylene glycol end-blocking PAG and acrylic or methacrylic acid, allyl alcohol Oxirane and/or propylene oxide adduct, the oxirane of isoprene alcohol and/or propylene oxide adduct, vinyl alcohol Oxirane and/or propylene oxide adduct, the oxirane of acrylic acid and/or propylene oxide adduct and methyl-prop The monomeric unit of monomer in the oxirane and/or propylene oxide adduct of olefin(e) acid.
(B) in the monomeric unit with alkylene oxide group of composition, the average addition of the alkylene oxide group of each monomeric unit Molal quantity is preferably more than 5, more preferably more than 7, more preferably more than 20 from the viewpoint of being improved from dispersiveness, and And preferably less than 150, more preferably less than 130.
In addition, as the monomeric unit with alkylene oxide group, the list of the monomer represented by following formulas (B1) is preferably come from Body unit.
【Chemical formula 5】
(in formula, R1bRepresent hydrogen atom or methyl.AO represents the alkylene oxide group of carbon number 2 or 3, and n is AO average addition mole Number, represent more than 5 and less than 150 number.Z represents ether (- O-) or ester group (- COO-).R2bRepresent hydrogen atom or carbon number more than 1 And less than 3 alkyl.〕
(B) concrete example of composition represents as follows.
(b1) comprising methacrylic acid and polymer of the methoxy poly (ethylene glycol) monomethacrylates as composition monomer
The polymer is formed in monomer from the viewpoint of dispersiveness improves, methacrylic acid be preferably 40 moles of % with Upper and 90 moles of below %.In addition, the polymer from the viewpoint of dispersiveness improves, is formed in monomer, the poly- second two of methoxyl group Alcohol monomethacrylates are preferably 10 moles of more than % and 60 mole of below %.In addition, the weight average molecular weight of the polymer from From the viewpoint of dispersiveness improves, preferably 10, more than 000 and 100, less than 000.Here, weight average molecular weight can be by solidifying Glue penetration chromatogram (standard substance：Single dispersing polyethylene glycol known to molecular weight) it is measured.
(b2) comprising polyoxyethylene list phenyl ether and formaldehyde condensation products of the phenoxetol phosphate as composition monomer
The polymer is formed in monomer, polyoxyethylene list phenyl ether is preferably 10 from the viewpoint of dispersiveness improves Mole more than % and 70 mole of below %.In addition, the polymer from the viewpoint of dispersiveness improves, is formed in monomer, benzene oxygen Base ethanol phosphate ester is preferably 30 moles of more than % and 90 mole of below %.In addition, the weight average molecular weight of the polymer is from scattered Property improve from the viewpoint of, preferably 5, more than 000 and 100, less than 000.Here, weight average molecular weight can pass through gel infiltration Chromatogram (standard substance：Single dispersing polyethylene glycol known to molecular weight) it is measured.
(b3) comprising methacrylic acid and polymer of the 2- hydroxyethylmethacry,ates as composition monomer
The polymer is formed in monomer from the viewpoint of dispersiveness improves, methacrylic acid be preferably 45 moles of % with Upper and 95 moles of below %.In addition, the polymer from the viewpoint of dispersiveness improves, is formed in monomer, 2- hydroxyethyls third Olefin(e) acid ester is preferably 5 moles of more than % and 55 mole of below %.In addition, what the weight average molecular weight of the polymer improved from dispersiveness Viewpoint is set out, and preferably 5, more than 000 and 100, less than 000.Here, weight average molecular weight can pass through gel permeation chromatography (mark Quasi- material：Single dispersing polyethylene glycol known to molecular weight) it is measured.
＜ (C) compositions ＞
〔(C1)〕
Compound (C1) is the compound represented by the formula (C1).
In formula (C1), R11It is to make as R11The HLB of-H compound is less than 5.10 alkyl.R11- H HLB is preferred For less than 3.21, more preferably less than 1.31, more preferably below -0.59, also, be preferably more than -3.46, more preferably For more than -2.51, more preferably more than -1.56.R11- H HLB is obtained by Davis (Davies) method.
R in formula (C1)11For alkyl.The alkyl includes the alkyl comprising substituent.
Atom or atomic group that substituent is that instead of the hydrogen atom of most basic organic compound and imported (chemical dictionary, The first edition, the 7th printing, the same people of (strain) Tokyo chemistry, on April 1st, 2003).Hydrocarbon comprising substituent can be the derivative of hydrocarbon Thing.Derivative refers to, when certain hydrocarbon is considered as parent, importing, oxidation, reduction, the substitution of atom through functional group etc. do not have The compound for significantly changing the change of the construction of parent and the degree of property and being formed.
As R11Alkyl, can enumerate alkyl, alkenyl, aralkyl, aryl, have substituent aryl (hereinafter referred to as take For aryl) etc..R11Alkyl be preferably selected from group in alkyl, alkenyl and substituted aryl.
R11Alkyl be preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, more preferably straight chain one-level Aliphatic alkyl.
R11Alkenyl be preferably aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl, more preferably straight chain one-level Aliphatic alkenyl.
Here, the one-level on alkyl or alkenyl refers to, in the carbon atom of the alkyl or alkenyl, is bonded with other groups Carbon atom is primary carbon atom.For example, with regard to R11For, in the carbon atom for referring to alkyl or alkenyl, the carbon atom being bonded with X is one Level carbon atom.
R11Substituted aryl be aromatic rings the aryl that is substituted with a substituent of hydrogen atom, the hydrogen atom quilt of aromatic rings can be enumerated The aryl of alkyl substitution.As substituted aryl, 1,2 or 3 of the hydrogen atom of aromatic rings can be enumerated by substituents such as alkyl The aryl substituted.The aryl of substituted aryl is preferably phenyl.And then carbon number more than 13 and less than 30 substitution virtue can be enumerated Base.
As substituted aryl, it is preferably more than 1, more preferably more than 2 that can enumerate selected from carbon number, also, is preferably Less than 10, in the phenyl of more preferably less than 8 alkyl-substituted phenyl, the phenyl of benzyl substitution and styrol Group.Substituted aryl can enumerate the group in the phenyl of the phenyl and styrol selected from benzyl substitution.
Substituted aryl is preferably selected from monobenzyl phenyl, dibenzylphenyl, tribenzyl phenyl, single styrenated phenyl, two Group in styrenated phenyl, tristyrenated phenyl, octyl phenyl and nonyl phenyl, more preferably selected from tribenzyl-benzene Group in base and distyrenated phenyl.
R11From the viewpoint of economy, preferably alkyl.
R11From the viewpoint of dissolving from water is easy, preferably alkenyl.
R11From the viewpoint of the viewpoint showed from the intensity of firming body and the foaming of suppression hydraulic-composition, preferably take For aryl.
R in formula (C4)11Carbon number more than 1 and less than 30 alkyl can specifically be enumerated.
R11Carbon number be preferably more than 8, more preferably more than 12, more preferably more than 16, also, preferably 22 with Under, more preferably less than 20, more preferably less than 18.
As R11Concrete example, can enumerate selected from carbon number be preferably more than 8, more preferably more than 10, further Preferably more than 16, also, preferably less than 22, more preferably less than 20 alkyl, and the hydrogen atom of the alkyl are taken For the group in the alkyl of base substitution.
As R11Other concrete examples, can enumerate selected from carbon number be preferably more than 8, more preferably more than 10, more enter One step is preferably more than 16, also, preferably less than 22, more preferably less than 20 alkyl or alkenyl and the alkyl or The group that the hydrogen atom of the alkenyl is substituted with a substituent, and aryl, carbon number more than 13 and less than 30 substitution of alkyl substitution Group in aryl.
As R11Other concrete examples, can enumerate and be selected from
Carbon number is preferably more than 8, is more preferably more than 10, is still more preferably more than 16, also, preferably 22 Below, be more preferably less than 20 alkyl, be preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, further Preferably straight chain Primary Fatty race alkyl, and
Carbon number is preferably more than 8, is more preferably more than 10, is still more preferably more than 16, also, preferably 22 Below, be more preferably less than 20 alkenyl, be preferably aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl, further Group preferably in straight chain Primary Fatty race alkenyl.
In addition, as R11Other concrete examples, can enumerate carbon number be preferably more than 1, more preferably more than 2, also, Preferably less than 10, more preferably less than 8 alkyl-substituted phenyl, phenyl, the phenyl of styrol of benzyl substitution. Specifically, these groups can enumerate the carbon number more than 13 selected from benzyl substitution and less than 27 phenyl and carbon number more than 14 and Group in less than 30 styrenated phenyls.
More specifically, as R11, can enumerate selected from for example, decyl, lauryl, myristyl, palmityl, tristearin Group in base, behenyl base, iso stearyl, oil base, tribenzyl phenyl, distyrenated phenyl and tristyrenated phenyl, from From the viewpoint of the mobility of hydraulic-composition improves, preferably enumerate selected from lauryl, myristyl, palmityl, tristearin Group in base, behenyl base, iso stearyl, oil base, tribenzyl phenyl and distyrenated phenyl, it may be more preferable to enumerate and be selected from Group in lauryl, myristyl, palmityl, stearyl, oil base, tribenzyl phenyl and distyrenated phenyl.
In formula (C1), X is O or COO, preferably O.
In formula (C2), AO is the alkylene oxide group of carbon number more than 1 and less than 4 alkylene oxide group, preferably carbon number 2 or 3.AO Preferably comprise the alkylene oxide group of carbon number 2.
In formula (C1), n1 is AO average addition molal quantity, is more than 0 and 300 from the viewpoint of cement dispersiveness Below.From the viewpoint of the mobility of hydraulic-composition improves, n1 is preferably more than 1, is more preferably more than 10, further Preferably more than 20, it is still more preferably more than 30, be still more preferably more than 40, is still more preferably more than 50, And from the interaction with (A) composition easily and it is economical from the viewpoint of, preferably less than 200, be more preferably less than 150, More preferably less than 100 number.
In formula (C1), M is counter ion counterionsl gegenions, and can enumerating hydrogen ion, alkali metal ion, alkaline-earth metal ion, (1/2 is former Son), ammonium ion etc..
From compound it is easy to manufacture from the viewpoint of, M is preferably ammonium ion.
From the viewpoint of the foul smell of compound, M is preferably alkali metal ion, is selected from sodium ion and potassium ion In alkali metal ion.
As compound (C1), the polyoxyethylene alkene ether sulphur of polyoxyethylene oleyl ether sulfuric ester compound etc. can be enumerated Acid esters compound or its salt, and the polyoxyethylene substituted aryl of distyrenated phenyl ether sulfuric ester compound of polyoxyethylene etc. Ether sulfuric ester compound or its salt.
〔(C2)〕
Compound (C2) is the compound represented by the formula (C2).
In formula (C2), R21It is to make as R21The HLB of-H compound is less than 5.10 alkyl.R21- H HLB is preferred For less than 3.21, more preferably less than 1.31, also, be preferably more than -3.46, more preferably more than -2.51, further preferably For it is more than -1.56, be still more preferably more than -0.60.R21- H HLB is obtained by Davis (Davies) method.
R in formula (C2)21For alkyl.The alkyl includes the alkyl comprising substituent.
Atom or atomic group that substituent is that instead of the hydrogen atom of most basic organic compound and imported (chemical dictionary, The first edition, the 7th printing, the same people of (strain) Tokyo chemistry, on April 1st, 2003).Hydrocarbon comprising substituent can be the derivative of hydrocarbon Thing.Derivative refers to, when certain hydrocarbon is considered as parent, importing, oxidation, reduction, the substitution of atom through functional group etc. do not have The compound for significantly changing the change of the construction of parent and the degree of property and being formed.
As R21Alkyl, can enumerate alkyl, alkenyl, aralkyl, aryl, have substituent aryl (hereinafter referred to as take For aryl) etc..R21Alkyl be preferably selected from group in alkyl, alkenyl and substituted aryl.
R21Alkyl be preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, more preferably straight chain one-level Aliphatic alkyl.
R21Alkenyl be preferably aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl, more preferably straight chain one-level Aliphatic alkenyl.
R21Substituted aryl be aromatic rings the aryl that is substituted with a substituent of hydrogen atom, the hydrogen atom quilt of aromatic rings can be enumerated The aryl of alkyl substitution.As substituted aryl, 1,2 or 3 of the hydrogen atom of aromatic rings can be enumerated by substituents such as alkyl The aryl substituted.The aryl of substituted aryl is preferably phenyl.And then carbon number more than 13 and less than 30 substitution virtue can be enumerated Base.
As substituted aryl, it is preferably more than 1, more preferably more than 2 that can enumerate selected from carbon number, also, is preferably Less than 10, in the phenyl of more preferably less than 8 alkyl-substituted phenyl, the phenyl of benzyl substitution and styrol Group.Substituted aryl can enumerate the group in the phenyl of the phenyl and styrol selected from benzyl substitution.
Substituted aryl is preferably selected from monobenzyl phenyl, dibenzylphenyl, tribenzyl phenyl, single styrenated phenyl, two Group in styrenated phenyl, tristyrenated phenyl, octyl phenyl and nonyl phenyl, more preferably selected from tribenzyl-benzene Group in base and distyrenated phenyl.
R21From the viewpoint of economy, preferably alkyl.
R21From the viewpoint of dissolving from water is easy, preferably alkenyl.
R21From the viewpoint of the viewpoint showed from the intensity of firming body and the foaming of suppression hydraulic-composition, preferably take For aryl.
In formula (C2), R21Carbon number more than 4 and less than 30 alkyl can specifically be enumerated.
R21Carbon number from dispersiveness improve from the viewpoint of, preferably more than 8, more preferably more than 12, further preferably For more than 16, also, preferably less than 22, more preferably less than 20, more preferably less than 18.
As R21Concrete example, can enumerate selected from carbon number be preferably more than 10, more preferably more than 12, also, excellent Elect less than 22 as, more preferably less than 20 alkyl, and the base in the alkyl that is substituted with a substituent of hydrogen atom of the alkyl Group.
As R21Other concrete examples, can enumerate selected from carbon number be preferably more than 10, more preferably more than 12, and And preferably less than 22, more preferably less than 20 alkyl or alkenyl and the hydrogen atom of the alkyl or the alkenyl are substituted Group in the group of base substitution, and the aryl of alkyl substitution, preferably carbon number more than 13 and less than 30 substituted aryl.
As R21Other concrete examples, can enumerate and be selected from：
Carbon number is preferably more than 10, more preferably more than 12, also, preferably less than 22, more preferably 20 Following alkyl, it is preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, more preferably straight chain Primary Fatty race Alkyl, and
Carbon number is preferably more than 10, more preferably more than 12, also, preferably less than 22, more preferably 20 Following alkenyl, it is preferably aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl, more preferably straight chain Primary Fatty race Group in alkenyl.
In addition, as R21Other concrete examples, can enumerate carbon number be preferably more than 1, more preferably more than 2, also, Preferably less than 10, more preferably less than 8 alkyl-substituted phenyl, phenyl, the phenyl of styrol of benzyl substitution. Specifically, these groups can enumerate the carbon number more than 13 selected from benzyl substitution and less than 27 phenyl and carbon number more than 14 and Group in less than 30 styrenated phenyl.
More specifically, as R21, can enumerate selected from for example, decyl, lauryl, myristyl, palmityl, tristearin Group in base, behenyl base, iso stearyl, oil base, tribenzyl phenyl, distyrenated phenyl and tristyrenated phenyl, from From the viewpoint of the mobility of hydraulic-composition improves, preferably enumerate selected from lauryl, myristyl, palmityl, tristearin Group in base, behenyl base, iso stearyl, oil base, tribenzyl phenyl and distyrenated phenyl, it may be more preferable to enumerate and be selected from Group in lauryl, myristyl, palmityl, stearyl, oil base, tribenzyl phenyl and distyrenated phenyl.
In formula (C2), X is O or COO, preferably O.
In formula (C2), AO is the alkylene oxide group of carbon number more than 2 and less than 4 alkylene oxide group, preferably carbon number 2 or 3.AO Preferably comprise the alkylene oxide group of carbon number 2.
In formula (C2), n2 is AO average addition molal quantity, is more than 1 and 300 from the viewpoint of cement dispersiveness Below.From the viewpoint of the mobility of hydraulic-composition improves, n2 is preferably more than 5, is more preferably more than 9, further Preferably more than 12, still more preferably for more than 20, be still more preferably more than 28, and from mutual with (A) composition Effect easily and it is economical from the viewpoint of, preferably less than 200, more preferably less than 150, more preferably less than 100, more More preferably less than 60, still more preferably it is less than 35.
In formula (C2), R22For hydrogen atom or carbon number more than 1 and less than 3 alkyl, preferably hydrogen atom.
As compound (C2), it is sub- that polyoxyethylene -2- ethylhexyls ether, polyoxyethylene decyl ethers, polyoxy can be enumerated The polyoxyethylene ether and polyoxyethylene alkene ether of Ethyl Lauroyl base ether, polyoxyethylene oleyl ether etc..In addition, it can lift Go out the polyoxyethylene ester of polyoxyethylene monostearate etc..In addition, can enumerate polyoxyethylene tribenzyl phenyl ether, The polyoxyethylene substituted aryl ether of the distyrenated phenyl ether of polyoxyethylene etc..
〔(C3)〕
Compound (C3) is the compound represented by the formula (C3).
In formula (C3), R31It is to make as R31The HLB of-H compound is less than 5.10 alkyl.R31- H HLB is preferred For less than 3.21, more preferably less than 1.31, also, be preferably more than -3.46, more preferably more than -2.51, further preferably For it is more than -1.56, be still more preferably more than -0.60.R31- H HLB is obtained by Davis (Davies) method.
R in formula (C3)31For alkyl.The alkyl includes the alkyl comprising substituent.
Atom or atomic group that substituent is that instead of the hydrogen atom of most basic organic compound and imported (chemical dictionary, The first edition, the 7th printing, the same people of (strain) Tokyo chemistry, on April 1st, 2003).Hydrocarbon comprising substituent can be the derivative of hydrocarbon Thing.Derivative refers to, when certain hydrocarbon is considered as parent, importing, oxidation, reduction, the substitution of atom through functional group etc. do not have The compound for significantly changing the change of the construction of parent and the degree of property and being formed.
As R31Alkyl, alkyl, alkenyl, aralkyl, aryl, the aryl etc. with substituent can be enumerated.Substituted aryl 1,2 or 3 substituted aryl of the hydrogen atom of aromatic rings can be enumerated.R31Alkyl be preferably selected from alkyl and alkenyl Group.
R31Alkyl be preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, more preferably straight chain one-level Aliphatic alkyl.
R31Alkenyl be preferably aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl, more preferably straight chain one-level Aliphatic alkenyl.
R31From the viewpoint of economy, preferably alkyl.
R31From the viewpoint of dissolving from water is easy, preferably alkenyl.
R in formula (C3)31Carbon number more than 4 and less than 30 alkyl can specifically be enumerated.
R31Carbon number can be preferably selected from more than 8, more preferably more than 12, more preferably more than 16, also, preferably For less than 22, more preferably less than 20, more preferably less than 18.
If enumerate R31Concrete example, then preferably enumerate selected from carbon number more than 10, more preferably more than 12, also, preferably It is substituted with a substituent for less than 27, more preferably less than 26, more preferably less than 24 alkyl, and the hydrogen atom of the alkyl Alkyl in group.
If enumerate R31Other concrete examples, then preferably enumerate selected from carbon number more than 10, more preferably more than 12, also, Preferably less than 27, it is more preferably less than 26, more preferably less than 24 alkyl or alkenyl, and the alkyl or the alkenyl Group in the group that hydrogen atom is substituted with a substituent.
If enumerate R31Other concrete examples, then preferably enumerate selected from carbon number more than 10, more preferably more than 12, also, Preferably less than 27, be more preferably less than 26, more preferably less than 24 alkyl, be preferably aliphatic alkyl, more preferably For straight-chain aliphatic alkyl, more preferably straight chain Primary Fatty race alkyl, and preferably carbon number more than 10, more preferably More than 12, also, preferably less than 27, more preferably less than 26, more preferably less than 24 alkenyl, preferably aliphatic Alkenyl, more preferably straight-chain aliphatic alkenyl, the group more preferably in straight chain Primary Fatty race alkenyl.
More specifically, as R31, can enumerate and be selected from decyl, lauryl, myristyl, palmityl, tristearin Group in base, behenyl base, iso stearyl and oil base, from the viewpoint of the mobility of hydraulic-composition improves, preferably The group in lauryl, myristyl, palmityl, stearyl, behenyl base, iso stearyl and oil base is enumerated, is more preferably lifted The group gone out in lauryl, myristyl, palmityl, stearyl and oil base.
In formula (C3), AO is the alkylene oxide group of carbon number more than 3 and less than 4 alkylene oxide group, preferably carbon number 2 or 3.AO Preferably comprise the alkylene oxide group of carbon number 2.
In formula (C3), n3 and n4 are identical or different, respectively AO average addition molal quantity, are more than 0 numbers.From water From the viewpoint of mud dispersiveness, n3 and n4's adds up to more than 1, is preferably more than 20, more preferably more than 50 number, also, From the viewpoint of economy, it is less than 300, is preferably less than 200, is more preferably less than 150, is more preferably less than 100 Number.
In formula (C3), R32And R33It is the identical or different, hydrogen atom of difference or carbon number more than 1 and less than 3 alkyl. R32And R33It is respectively preferably hydrogen atom.
〔(C4)〕
Compound (C4) is the compound represented by the formula (C4).
In formula (C4), R41It is to make as R41The HLB of-H compound is less than 5.10 alkyl.R41- H HLB is preferred For less than 3.21, more preferably less than 1.31, also, be preferably more than -3.46, more preferably more than -2.51, further preferably For it is more than -1.56, be still more preferably more than -0.60.R41- H HLB is obtained by Davis (Davies) method.
R in formula (C4)41For alkyl.The alkyl includes the alkyl comprising substituent.
Atom or atomic group that substituent is that instead of the hydrogen atom of most basic organic compound and imported (chemical dictionary, The first edition, the 7th printing, the same people of (strain) Tokyo chemistry, on April 1st, 2003).Hydrocarbon comprising substituent can be the derivative of hydrocarbon Thing.Derivative refers to, when certain hydrocarbon is considered as parent, importing, oxidation, reduction, the substitution of atom through functional group etc. do not have The compound for significantly changing the change of the construction of parent and the degree of property and being formed.
As R41Alkyl, alkyl, alkenyl, aralkyl, aryl, the aryl etc. with substituent can be enumerated.Substituted aryl 1,2 or 3 substituted aryl of the hydrogen atom of aromatic rings can be enumerated.R41Alkyl be preferably selected from alkyl and alkenyl Group.
R41Alkyl be preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, more preferably straight chain one-level Aliphatic alkyl.
R41Alkenyl be preferably aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl, more preferably straight chain one-level Aliphatic alkenyl.
R41From the viewpoint of economy, preferably alkyl.
R41From the viewpoint of dissolving from water is easy, preferably alkenyl.
R in formula (C4)41Carbon number more than 4 and less than 30 alkyl can specifically be enumerated.
R41Carbon number can preferably select more than 8, more preferably more than 12, more preferably more than 16, also, preferably For less than 22, more preferably less than 20, more preferably less than 18.
If enumerate R41Concrete example, then preferably enumerate selected from carbon number more than 10, more preferably more than 12, also, preferably It is substituted with a substituent for less than 27, more preferably less than 26, more preferably less than 24 alkyl, and the hydrogen atom of the alkyl Alkyl in group.
If enumerate R41Other concrete examples, then preferably enumerate selected from carbon number more than 10, more preferably more than 12, also, Preferably less than 27, it is more preferably less than 26, more preferably less than 24 alkyl or alkenyl, and the alkyl or the alkenyl Group in the group that hydrogen atom is substituted with a substituent.
If enumerate R41Other concrete examples, then preferably enumerate selected from carbon number more than 10, more preferably more than 12, also, Preferably less than 27, be more preferably less than 26, more preferably less than 24 alkyl, be preferably aliphatic alkyl, more preferably For straight-chain aliphatic alkyl, more preferably straight chain Primary Fatty race alkyl, and preferably carbon number more than 10, more preferably More than 12, also, preferably less than 27, more preferably less than 26, more preferably less than 24 alkenyl, preferably aliphatic Alkenyl, more preferably straight-chain aliphatic alkenyl, the group more preferably in straight chain Primary Fatty race alkenyl.
More specifically, as R41, can enumerate and be selected from decyl, lauryl, myristyl, palmityl, tristearin Group in base, behenyl base, iso stearyl and oil base, from the viewpoint of the mobility of hydraulic-composition improves, preferably The group in lauryl, myristyl, palmityl, stearyl, behenyl base, iso stearyl and oil base is enumerated, is more preferably lifted The group gone out in lauryl, myristyl, palmityl, stearyl and oil base.
In formula (C4), AO is the alkylene oxide group of carbon number more than 2 and less than 4 alkylene oxide group, preferably carbon number 2 or 3.AO Preferably comprise the alkylene oxide group of carbon number 2.
In formula (C4), Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M.M is Counter ion counterionsl gegenions, hydrogen ion, alkali metal ion, alkaline-earth metal ion (1/2 atom), ammonium ion etc. can be enumerated.From compound From the viewpoint of easy to manufacture, M is preferably ammonium ion.From the viewpoint of the foul smell of compound, M be preferably alkali metal ion, Alkali metal ion more preferably in sodium ion and potassium ion.
In formula (C4), n5 and n6 distinguish identical or different AO average addition molal quantity, are more than 0 numbers.n5For 0 In the case of, Y1For hydrogen atom, n6In the case of 0, Y2For hydrogen atom.From the viewpoint of cement dispersiveness, n5 and n6 conjunction It is calculated as more than 1, is preferably more than 20, more preferably more than 50 number, also, is less than 300, excellent from the viewpoint of economy Elect less than 200 as, be more preferably less than 150, more preferably less than 100 number.n5And n6It is asynchronously 0.Therefore compound (C4) there is (AO)n5-SO3M and (AO)n6-SO3At least the 1 of M.
As compound (C4), the aliphatic amine alkylidene of tallow amine ethylene oxide adduct sulfuric ester compound etc. can be enumerated The sulfuric ester compound of addition product.
(C) composition can also be the change for belonging to compound (C1), compound (C2), compound (C3) and compound (C4) More than a kind of compound.(C) composition is from the viewpoint of dispersiveness, 1 be preferably selected from compound (C1) and compound (C4) The compound of the kind above.In addition, (C) composition is preferably selected from compound (C3) and compound from the viewpoint of air capacity control (C4) more than a kind of compound in.In addition, (C) composition from the viewpoint of economy, be preferably selected from compound (C1) and More than a kind of compound in compound (C3).
The ＞ such as the composition of ＜ dispersant for hydraulic composition compositions
In the solid constituent of the dispersant for hydraulic composition composition of the present invention, the mass % of (A) composition 1 is preferably comprised More than, more preferably more than 3 mass %, further preferred more than 5 mass %, also, preferably below 99 mass %, more preferably 97 matter Measure below %, further preferred below 95 mass %.
It should be noted that on dispersant for hydraulic composition composition, solid constituent refers to the composition beyond water.
In the solid constituent of the dispersant for hydraulic composition composition of the present invention, the mass % of (B) composition 1 is preferably comprised More than, more preferably more than 3 mass %, further preferred more than 5 mass %, also, preferably below 95 mass %, more preferably 90 matter Measure below %, further preferred below 80 mass %.
In the solid constituent of the dispersant for hydraulic composition composition of the present invention, the mass % of (C) composition 2 is preferably comprised More than, more preferably more than 5 mass %, further preferred more than 7 mass %, also, preferably below 90 mass %, more preferably 80 matter Measure below %, further preferred below 70 mass %.
From the viewpoint of the mobility reduced to hydraulic-composition assigns the temperature dependency of effect, water of the invention In hydraulic composition dispersant composition, the mass ratio in terms of (A)/(B) preferably more than 0.01 of (A) composition and (B) composition, More preferably more than 0.05, it is more preferably more than 0.1, be still more preferably more than 0.3, is still more preferably 1.0 More than, still more preferably be more than 3.0, also, preferably less than 100, more preferably less than 55, more preferably 10 with Under, still more preferably be less than 5.
From dispersiveness improve from the viewpoint of, in dispersant for hydraulic composition composition of the invention, (A) composition with (C) mass ratio of composition in terms of (A)/(C) be preferably more than 0.1, more preferably more than 0.2, more preferably more than 0.3, Still more preferably for more than 0.4, be still more preferably more than 0.5, also, preferably less than 30, more preferably less than 20, More preferably less than 10, still more preferably it is less than 5.
From dispersiveness improve from the viewpoint of, in dispersant for hydraulic composition composition of the invention, (A) composition and (B) mass ratio of total and (C) composition of composition be preferably more than 0.01 by (C)/((A)+(B)) in terms of, be more preferably 0.02 with Above, it is more preferably more than 0.05, be still more preferably more than 0.1, is still more preferably more than 0.3, further Preferably more than 0.4, still more preferably it is more than 0.6, also, preferably less than 10, is more preferably less than 7, is further excellent Elect less than 5 as, be still more preferably less than 4, be still more preferably less than 2, be still more preferably less than 1, more enter one Step is preferably less than 0.8.
The dispersant for hydraulic composition composition of the present invention can further contain (D) defoamer (hereinafter referred to as (D) composition).
As (D) composition, the ether system beyond silicone-based defoamer, fatty acid ester system defoamer, (C) composition can be enumerated More than a kind in defoamer, poly (oxyalkylene) base system defoamer, alkyl phosphate system defoamer and acetylenic glycols system defoamer disappears Infusion.
As (D) composition, the ether system being preferably selected from beyond silicone-based defoamer, fatty acid ester system defoamer and (C) composition More than a kind of defoamer in defoamer.
Silicone-based defoamer is preferably dimethyl polysiloxane.
Fatty acid ester system defoamer is preferably polyalkylene glycol fatty acid esters.
Ether system defoamer is preferably alkyl ether.
Poly (oxyalkylene) base system defoamer is preferably the block copolymer of oxirane and expoxy propane.
In alkyl phosphoric acid system defoamer, preferably tributyl phosphate, three iso-butyl ester of phosphoric acid, octyl phosphate sodium.
Preferred 2,4,7,9- tetramethyl -5- decine -4,7- glycol or its alkylene oxide addition product in acetylenic glycols system defoamer.
As (D) composition, from the viewpoint of it can be reduced with inhibition strength, preferred fat acid esters system defoamer.
Silicone-based defoamer preferably has the emulsifying of intermiscibility with water.Silicone-based as the emulsifying for having intermiscibility with water The commercially available product of defoamer, KM-70, KM-73A (being SHIN-ETSU HANTOTAI's silicone (strain)), TSA series (Momentive can be enumerated Performance Materials Japan LLC), FS ANTIFOAM serial (Dong Li-DOW CORNING (strain)), ANTIFOAM E- 20 (flower kings (strain)) etc..
As the commercially available product of the polyalkylene glycol fatty acid esters of fatty acid ester system defoamer, RHEODOL TW- can be enumerated L120 (flower king (strain)), Nicofix, FOAMLEX (being that solar corona is chemical (strain)) etc..
As the commercially available product of the alkyl ether of ether system defoamer, defoamer No.1, defoamer can be enumerated No.5 (being colored king (strain)), Adeka Pluronic series ((strain) Adeka) etc..
, can as the commercially available product of the block copolymer of the PEO PPOX in poly (oxyalkylene) base system defoamer Enumerate the block copolymer of oxirane and expoxy propane, such as PLURONIC (trade mark) product (BASF AG) etc..
As the commercially available product of acetylenic glycols system defoamer, the series of SURFYNOL (trade mark) 400 (Air Products can be enumerated And Chemicals, Inc.) etc..
In the solid constituent of the dispersant for hydraulic composition composition of the present invention, the matter of (D) composition 0.001 is preferably comprised Measure more than %, more preferably more than 0.01 mass %, further preferred more than 0.1 mass %, also, preferably below 10 mass %, More preferably below 5 mass %, further preferred below 1 mass %.
From foaming suppress and defoaming from the viewpoint of, in dispersant for hydraulic composition composition of the invention, (C) into By (D)/(C) in terms of it is preferably more than 0.00001 point with the mass ratio of (D) composition, is more preferably more than 0.00005, is further excellent Elect more than 0.0001, also, preferably less than 0.5, more preferably less than 0.1, more preferably less than 0.05 as.
The dispersant for hydraulic composition composition of the present invention can contain conventional cement dispersants, water-soluble high score Sub- compound, air entraining agent, cement wetting agents, swelling agent, waterproofing agent, delay agent, accelerator, thickener, flocculating agent, dry reduction The compositions such as agent, intensity enhancer, curing accelerator, preservative (except (A)~(D) compositions).
The present invention dispersant for hydraulic composition composition form can be liquid, solid it is any.This hair In the case that bright dispersant for hydraulic composition composition is liquid, water is preferably comprised.The hydraulic-composition of the present invention Can be the composition of 1 formulation containing (A) composition, (B) composition and (C) composition with dispersant composition.The hydraulic of the present invention Property composition dispersant composition can also be containing (A) composition, (B) composition, (C) composition and in addition arbitrary The composition of 1 formulation of composition.
From the viewpoint of workability when preparing hydraulic-composition, dispersant for hydraulic composition composition be containing Have the content of the water of the situation of the liquid of water be preferably more than 10 mass %, more preferably 30 mass % in the composition with Upper, more preferably more than 50 mass %, also, from the viewpoint of the mobility for improving hydraulic-composition, be preferably Below 90 mass %, more preferably below 70 mass %.
From improve hydraulic-composition mobility from the viewpoint of, dispersant for hydraulic composition composition be containing The content of (A) composition of the situation of the liquid of water in the composition be preferably more than 1 mass %, more preferably 4 mass % with Upper, more preferably more than 7 amount %, also, preferably below 50 mass %, it is more preferably below 32 mass %, further Preferably below 27 mass %.
From improve hydraulic-composition mobility from the viewpoint of, dispersant for hydraulic composition composition be containing The content of (B) composition of the situation of the liquid of water in the composition be preferably more than 1 mass %, more preferably 4 mass % with Upper, more preferably more than 7 mass %, also, preferably below 60 mass %, more preferably below 50 mass %, enter one Step is preferably below 32 mass %.
From improve hydraulic-composition mobility from the viewpoint of, dispersant for hydraulic composition composition be containing The content of (C) composition of the situation of the liquid of water in the composition be preferably more than 1 mass %, more preferably 4 mass % with Upper, more preferably more than 7 mass %, also, preferably below 60 mass %, more preferably below 50 mass %, enter one Step is preferably below 32 mass %.
From improve hydraulic-composition mobility from the viewpoint of, dispersant for hydraulic composition composition be containing Total content of (A) composition of the situation of the liquid of water, (B) composition and (C) composition is preferably 10 matter in the composition Measure more than %, more preferably more than 20 mass %, more preferably more than 30 mass %, also, preferably 90 mass % with Under, more preferably below 70 mass %, more preferably below 50 mass %.
As the present invention dispersant for hydraulic composition composition, can enumerate containing：
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) hydraulicity combination of more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by Thing dispersant composition.
【Chemical formula 6】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11、R21、R31、R41It is identical or different, carbon number more than 4 and less than 30 alkyl are represented respectively,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
(inorganic particle dispersant composition)
(A) composition used, (B) composition are specific with (C) composition in the inorganic particle dispersant composition of the present invention Example and preferred embodiment are identical with described in the dispersant for hydraulic composition composition of the present invention respectively.In addition, this The inorganic particle dispersant composition of invention can contain the defoamer of (D) composition.(D) concrete example of composition and it is preferable to carry out Mode is identical with described in the dispersant for hydraulic composition composition of the present invention respectively.
As inorganic particle, it is not particularly limited, following material can be enumerated.In inorganic particle, relative to hydraulicity powder Body uses the dispersant for hydraulic composition composition of the present invention.
(1) hydraulic powder such as cement, gypsum；
(2) flyash, silicon ash, volcanic ash, silicic acid carclazyte etc. have the powder of pozzolanic action；
(3) the latent hydraulicity powder such as coal ash, blast-furnace slag, diatomite；
(4) silicate such as kaolin, alumina silicate, clay, talcum, mica, calcium silicates, sericite, bentonite；
(5) carbonate such as calcium carbonate, magnesium carbonate, barium carbonate, basic lead carbonate；
(6) sulfate such as calcium sulfate, barium sulfate；
(7) chromate such as strontium chromate, pigment yellow；
(8) molybdate such as zinc molybdate, calcium molybdate zinc, magnesium molybdate；
(9) aluminum oxide, antimony oxide, titanium oxide, cobalt oxide, ferroso-ferric oxide, di-iron trioxide, lead orthoplumbate, an oxygen Change the metal oxides such as lead, chrome oxide green, tungstic acid, yittrium oxide；
(10) metal hydroxides such as aluminium hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide, metatitanic acid；
(11) metal carbides such as carborundum, tungsten carbide, boron carbide, titanium carbide；
(12) aluminium nitride, silicon nitride, boron nitride, zirconium oxide, barium titanate, satin white, carbon black, graphite, chrome yellow, mercuric sulphide, Ultramarine, dark purple, titan yellow, chrome vermilion, lithopone, copper acetoarsenite, nickel, silver, palladium, lead zirconate titanate etc. are unfiled above-mentioned (1) other inorganic particles in~(11).
The inorganic particle dispersant composition of the present invention can be used in inorganic particle slurry.Inorganic particle slurry is to contain There is the slurry of inorganic particle, water, (A) composition, (B) composition and (C) composition.When inorganic particle is hydraulic powder, slurry is this The hydraulic-composition of invention.
Concrete example and the preferred embodiment difference of (A) composition, (B) composition and (C) composition used in the slurry of the present invention It is identical with described in the dispersant for hydraulic composition composition of the present invention.
As inorganic particle slurry, it can enumerate and for example use the slurry of blast-furnace slag (hereinafter referred to as inorganic particle Blast-furnace slag slurry).Blast-furnace slag slurry preferably comprises the present invention relative to the mass parts of blast-furnace slag 100 in terms of solid constituent Inorganic particle with more than the mass parts of dispersant composition 0.01 and 5.0 mass parts.Blast-furnace slag slurry is relative to blast-furnace slag 100 mass parts, preferably comprise more than the mass parts of water 40, more preferably more than 45 mass parts, also, preferably 250 mass parts, more preferably Below 230 mass parts.In addition, blast-furnace slag slurry preferably comprises (D) composition.In blast-furnace slag slurry, (C) composition and (D) into The mass ratio divided is preferably more than 0.00001, more preferably more than 0.00005, more preferably 0.0001 in terms of (D)/(C) More than, also, preferably less than 0.5, more preferably less than 0.1, more preferably less than 0.05.
(hydraulic-composition)
The present invention provides the hydraulic-composition containing hydraulic powder, water, (A) composition, (B) composition and (C) composition. (A) composition, (B) composition and (C) composition can add dispersant for hydraulic composition composition use of the invention so as to make Standby hydraulic-composition, can also each it be added separately in the system comprising hydraulic powder and water so as to prepare hydraulicity group Compound.
The hydraulic powder used in the hydraulic-composition of the present invention refers to there is what is hardened by hydration reaction The powder of physical property, cement, gypsum etc. can be enumerated.Preferably Portland cement, belite cement, moderate heat cement, early strong water The cement such as mud, super-early strength cement, sulfate-resistant cement.Alternatively, it is also possible to being that blast-furnace slag, fine coal are with the addition of into cement etc. The blast furnace slag cement of the powder with pozzolanic action and/or latent hydraulicity such as ash, silicon ash, stone flour (calcium carbonate powder) etc., Pulverized fuel ash cement, Silica fume cement etc..
Water/hydraulic powder ratio (quality hundred of water and hydraulic powder in slurry of the hydraulic-composition of the present invention Divide rate (quality %), be generally simply denoted as W/P, in the case where powder is cement, be simply denoted as W/C.Even if) a small amount of from coordinating Water can also show to set out in terms of the mobility of hydraulic-composition, preferably more than 15 mass %, be more preferably 20 matter Measure more than %, also, preferably below 50 mass %, more preferably below 45 mass %, more preferably 40 mass % with Under.
(A) composition used in the hydraulic-composition of the present invention, the concrete example of (B) composition and (C) composition and preferred real It is identical with described in the dispersant for hydraulic composition composition of the present invention respectively to apply mode.
In the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, (A) composition 0.01 is preferably comprised More than mass parts, more preferably more than 0.03 mass parts, it is more than further preferred 0.05 mass parts, still more preferably 0.1 mass More than part, still more preferably more than 0.15 mass parts, still more preferably more than 0.30 mass parts, also, preferably 2 mass parts Below, more preferably below 1.5 mass parts, below further preferred 1.0 mass parts, still more preferably below 0.80 mass parts.
In the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, (B) composition 0.005 is preferably comprised More than mass parts, more preferably more than 0.03 mass parts, it is more than further preferred 0.05 mass parts, still more preferably 0.1 mass More than part, still more preferably more than 0.15 mass parts, still more preferably more than 0.2 mass parts, also, preferably 3 mass parts Below, enter more preferably below 2 mass parts, below further preferred 1.5 mass parts, still more preferably below 1.0 mass parts, more One step is preferably below 0.7 mass parts, still more preferably below 0.5 mass parts.
In the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, (C) composition 0.01 is preferably comprised More than mass parts, more preferably more than 0.02 mass parts, it is more than further preferred 0.04 mass parts, still more preferably 0.06 mass More than part, still more preferably more than 0.08 mass parts, still more preferably more than 0.1 mass parts, still more preferably 0.3 matter Measure part more than, also, preferably below 2 mass parts, more preferably below 1.5 mass parts, below further preferred 1.3 mass parts, more Below further preferred 1 mass parts, still more preferably below 0.8 mass parts, still more preferably below 0.6 mass parts.
In the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, (A) composition and (B) are preferably comprised More than into the mass parts of subtotaling 0.005, more preferably more than 0.03 mass parts, it is more than further preferred 0.1 mass parts, further It is preferred that more than 0.15 mass parts, still more preferably more than 0.3 mass parts, also, preferably below 5 mass parts, more preferably 3 mass Below part, below further preferred 2 mass parts, still more preferably below 1 mass parts.
In the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, (A) composition, (B) are preferably comprised More than total 0.01 mass parts of composition and (C) composition, more preferably more than 0.05 mass parts, further preferred 0.1 mass parts with It is upper, still more preferably more than 0.14 mass parts, still more preferably more than 0.20 mass parts, still more preferably 0.40 mass More than part, still more preferably more than 0.70 mass parts, also, preferably below 5 mass parts, more preferably below 4 mass parts, enter one Step is preferably below 3 mass parts, still more preferably below 2 mass parts, still more preferably below 1.5 mass parts.
From the viewpoint of temperature dependency is reduced, in hydraulic-composition of the invention, (A) composition and (B) composition Mass ratio is preferably more than 0.01 in terms of (A)/(B), is more preferably more than 0.05, is more preferably more than 0.1, further Preferably more than 0.3, it is still more preferably more than 1.0, is still more preferably more than 3.0, also, preferably less than 100, More preferably less than 55, it is more preferably less than 10, is still more preferably less than 5.
From the viewpoint of dispersiveness improves, in hydraulic-composition of the invention, the quality of (A) composition and (C) composition Than in terms of (A)/(C) be preferably more than 0.1, more preferably more than 0.2, more preferably more than 0.3, be still more preferably More than 0.4, still more preferably it is more than 0.5, also, preferably less than 30, more preferably less than 20, more preferably 10 Below, still more preferably it is less than 5.
From the viewpoint of dispersiveness improves, in hydraulic-composition of the invention, (A) composition is total with (B) composition Mass ratio with (C) composition is preferably more than 0.01 in terms of (C)/((A)+(B)), is more preferably more than 0.02, further preferably For more than 0.05, be still more preferably more than 0.1, be still more preferably more than 0.3, be still more preferably more than 0.4, Still more preferably it is more than 0.6, also, preferably less than 10, be more preferably less than 7, be more preferably less than 5, more enters One step is preferably less than 4, be still more preferably less than 2, be still more preferably less than 1, be still more preferably 0.8 with Under.
The hydraulic-composition of the present invention can further contain defoamer and be used as (D) composition.The concrete example of defoamer and Preferred embodiment is identical with described in the dispersant for hydraulic composition composition of the present invention.Use the feelings of (D) composition Under condition, in hydraulic-composition of the invention, relative to the mass parts of hydraulic powder 100, (D) composition 0.00005 is preferably comprised More than mass parts, more preferably more than 0.00025 mass parts, more than further preferred 0.0005 mass parts, also, preferably 0.1 matter Measure below part, more preferably below 0.075 mass parts, below further preferred 0.05 mass parts.The sight for suppressing from foaming and defoaming Point sets out, and in hydraulic-composition of the invention, the mass ratio of (C) composition and (D) composition is preferably in terms of (D)/(C) More than 0.00001, be more preferably more than 0.00005, more preferably more than 0.0001, also, preferably less than 0.5, more Preferably less than 0.1, it is more preferably less than 0.05.
The hydraulic-composition of the present invention preferably comprises aggregate.As aggregate, can enumerate in fine aggregate and coarse aggregate Aggregate.As fine aggregate, can enumerate in JIS A0203-2014 with aggregate as defined in designation 2311.As fine aggregate, can lift Go out river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their broken sand, blast-furnace slag fine aggregate, ferronickel slag fine aggregate, Lightweight fine aggregate (artificial and natural) and recycled fine aggregate etc..In addition, as coarse aggregate, can enumerate in JIS A0203-2014 with Aggregate as defined in designation 2312.As coarse aggregate, can enumerate for example, river sand gravel, land gravel, mountain gravel, sea sand gravel, lime sand Gravel, their rubble, blast-furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and regenerated coarse aggregate Deng.Different types of fine aggregate, coarse aggregate can be used in mixed way, the aggregate of single kind can also be used.
In the case that hydraulic-composition is concrete, from the hydraulic such as the intensity of performance hydraulic-composition and reduction cement The usage amount of property powder, improve to from the viewpoint of the fillibility of template etc., the loose volume of the usage amount of coarse aggregate is preferably More than 50%, it is more preferably more than 55%, more preferably more than 60%, also, preferably less than 100%, is more preferably Less than 90%, it is more preferably less than 80%.Loose volume is 1m3The ratio of the volume (including space) of coarse aggregate in concrete Example.
In addition, in the case that hydraulic-composition is concrete, from improving to from the viewpoint of the fillibility of template etc., carefully The usage amount of aggregate is preferably 500kg/m3Above, more preferably 600kg/m3Above, more preferably 700kg/m3More than, Also, preferably 1000kg/m3Below, it is more preferably 900kg/m3Below.
In the case that hydraulic-composition is mortar, the usage amount of fine aggregate is preferably 800kg/m3Above, more preferably 900kg/m3Above, more preferably 1000kg/m3More than, also, preferably 2000kg/m3Below, more preferably 1800kg/m3Below, it is more preferably 1700kg/m3Below.
As hydraulic-composition, concrete etc. can be enumerated.The concrete of cement is wherein preferably used.The water of the present invention Hydraulic composition Self-leveling is used, used for refractory material, gypsum is used, lightweight or heavy concrete is used, AE is used, repairing is used, prepackage is used, Perfusion is used, foundation improvement is used, grouting is used, cold snap with etc. be useful in any field.
The hydraulic-composition of the present invention can further contain other compositions.Can enumerate for example, AE agent, delay agent, rise Infusion, thickener, foaming agent, waterproofing agent, fluidizing reagent etc. (except suitable with (A)~(D) compositions).
As the present invention hydraulic-composition, can enumerate containing：
Hydraulic powder,
Water,
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) hydraulicity combination of more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by Thing.
【Chemical formula 7】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11、R21、R31、R41It is identical or different, carbon number more than 4 and less than 30 alkyl are represented respectively,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
(manufacture method of dispersant for hydraulic composition composition)
The present invention provides mix (A) composition, (B) composition and (C) composition, dispersant for hydraulic composition composition Manufacture method.
(A) composition used in the manufacture method of the dispersant for hydraulic composition composition of the present invention, (B) composition and (C) concrete example of composition and preferred embodiment respectively with the dispersant for hydraulic composition composition of the present invention described in phase Together.And then by (A) composition, (B) composition, (C) composition and (D) composition mix, can also manufacture containing (A) composition, (B) into Divide, the dispersant for hydraulic composition composition of (C) composition and (D) composition.(D) concrete example and preferred embodiment of composition It is identical with described in the dispersant for hydraulic composition composition of the present invention respectively.
In addition, the item described in the dispersant for hydraulic composition composition of the present invention can compatibly be used in this In the manufacture method of the dispersant for hydraulic composition composition of invention.
Hydraulicity group of the manufacture method of the dispersant for hydraulic composition composition of the present invention as the manufacture present invention Compound is suitable with the method for dispersant composition.
As the present invention dispersant for hydraulic composition composition manufacture method, can enumerate containing (A) composition, (B) manufacture method of the dispersant for hydraulic composition composition of composition, (C) composition and water.In this case, (A) composition, (B) mixing of composition, (C) composition and water can be carried out by the arbitrary method in the range of performance is not reduced.For example, The aqueous solution of (A) composition more than freezing point that can be by will warm up (C) composition, be heated to the freezing point of (C) composition with On (B) composition the aqueous solution and the method that is mixed with mixer of (C) composition, make (A) composition, (B) composition and (C) into Method that is soluble in water respectively and mixing the aqueous solution of the aqueous solution of (A) composition, the aqueous solution of (B) composition and (C) composition Come carry out.
(manufacture method of hydraulic-composition)
The present invention provides the hydraulic-composition for mixing hydraulic powder, water, (A) composition, (B) composition and (C) composition Manufacture method.
(A) composition used, (B) composition are specific with (C) composition in the manufacture method of the hydraulic-composition of the present invention Example and preferred embodiment are identical with described in the dispersant for hydraulic composition composition of the present invention respectively.
In addition, the concrete example of hydraulic powder used in the manufacture method of the hydraulic-composition of the present invention and preferred real It is identical with described in the hydraulic-composition of the present invention to apply mode.
And then hydraulic powder, water, (A) composition, (B) composition, (C) composition and (D) composition can be mixed, so as to make Make the dispersant for hydraulic composition group containing hydraulic powder, water, (A) composition, (B) composition, (C) composition and (D) composition Compound.(D) concrete example of composition and preferred embodiment the dispersant for hydraulic composition composition institute with the present invention respectively That states is identical.
In addition, the item described in the dispersant for hydraulic composition composition and hydraulic-composition of the present invention can To be suitably employed in the manufacture method of the hydraulic-composition of the present invention.
In the manufacture method of the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, preferably mix (A) more than the mass parts of composition 0.01, more preferably more than 0.03 mass parts, more than further preferred 0.05 mass parts, further It is preferred that more than 0.1 mass parts, still more preferably more than 0.15 mass parts, still more preferably more than 0.30 mass parts, also, It is preferred that below 2 mass parts, more preferably below 1.5 mass parts, below further preferred 1.0 mass parts, still more preferably 0.80 Below mass parts.
In the manufacture method of the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, preferably mix (B) more than the mass parts of composition 0.005, more preferably more than 0.03 mass parts, more than further preferred 0.05 mass parts, further It is preferred that more than 0.1 mass parts, still more preferably more than 0.15 mass parts, still more preferably more than 0.2 mass parts, also, It is preferred that below 3 mass parts, more preferably below 2 mass parts, below further preferred 1.5 mass parts, still more preferably 1.0 mass Below part, still more preferably below 0.7 mass parts, still more preferably below 0.5 mass parts.
In the manufacture method of the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, preferably mix (C) more than the mass parts of composition 0.01, more preferably more than 0.02 mass parts, more than further preferred 0.04 mass parts, further It is preferred that more than 0.06 mass parts, still more preferably more than 0.08 mass parts, still more preferably enter more than 0.1 mass parts, more One step is preferably more than 0.3 mass parts, also, preferably below 2 mass parts, more preferably below 1.5 mass parts, further preferred 1.3 Below mass parts, still more preferably below 1 mass parts, still more preferably below 0.8 mass parts, still more preferably 0.6 Below mass parts.
In the manufacture method of the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, preferably mix (A) composition and (B) into more than the mass parts of subtotaling 0.005, more preferably more than 0.03 mass parts, further preferred 0.1 mass parts More than, still more preferably more than 0.15 mass parts, still more preferably more than 0.3 mass parts, also, preferably 5 mass parts with Under, more preferably below 3 mass parts, below further preferred 2 mass parts, still more preferably below 1 mass parts.
In the manufacture method of the hydraulic-composition of the present invention, relative to the mass parts of hydraulic powder 100, preferably mix (A) more than total 0.01 mass parts of composition, (B) composition and (C) composition, more preferably more than 0.05 mass parts, further preferably More than 0.1 mass parts, still more preferably more than 0.14 mass parts, still more preferably more than 0.20 mass parts, further It is preferred that more than 0.40 mass parts, still more preferably more than 0.70 mass parts, also, preferably below 5 mass parts, more preferably 4 matter Measure part below, below further preferred 3 mass parts, still more preferably below 2 mass parts, still more preferably 1.5 mass parts Below.
The present invention hydraulic-composition manufacture method in, from reduce temperature dependency from the viewpoint of, mixing (A) into Divide and (B) composition so that (A)/(B) mass ratio is preferably more than 0.01, is more preferably more than 0.05, more preferably More than 0.1, it is still more preferably more than 0.3, be still more preferably more than 1.0, is still more preferably more than 3.0, and And preferably less than 100, more preferably less than 55, more preferably less than 10, still more preferably be less than 5.
In the manufacture method of the hydraulic-composition of the present invention, from the viewpoint of dispersiveness improves, mixing (A) composition, (B) composition and (C) composition so that the total and mass ratio of (C) composition of (A) composition and (B) composition is in terms of (C)/((A)+(B)) Preferably more than 0.01, be more preferably more than 0.02, more preferably more than 0.05, still more preferably for more than 0.1, more More preferably more than 0.3, it is still more preferably more than 0.4, is still more preferably more than 0.6, also, preferably 10 Below, be more preferably less than 7, more preferably less than 5, still more preferably for less than 4, be still more preferably less than 2, It is still more preferably less than 1, is still more preferably less than 0.8.
In the manufacture method of the hydraulic-composition of the present invention, the defoamer as (D) composition can be further mixed.Disappear The concrete example and preferred embodiment of infusion are identical with described in the dispersant for hydraulic composition composition of the present invention.Make In the case of with (D) composition, in the manufacture method of hydraulic-composition of the invention, relative to the mass parts of hydraulic powder 100, It is preferred that mix more than the mass parts of (D) composition 0.00005, more preferably more than 0.00025 mass parts, further preferred 0.0005 mass More than part, also, preferably below 0.1 mass parts, more preferably below 0.075 mass parts, below further preferred 0.05 mass parts.
In the manufacture method of the hydraulic-composition of the present invention, from by (A) composition, (B) composition and (C) composition and cement etc. From the viewpoint of hydraulic powder successfully mixes, preferably (A) composition, (B) composition, (C) composition are mixed with water in advance, then with Hydraulic powder mixes.The dispersant for hydraulic composition composition of the invention containing water can be used.
In addition, in the manufacture method of the hydraulic-composition of the present invention, preferably by the hydraulic powder of cement etc. and this hair The method of bright dispersant for hydraulic composition composition mixing.The dispersant for hydraulic composition composition of the present invention can To be powder or liquid, preferably with respect to hydraulic powder, with above-mentioned addition addition (A) composition, (B) composition, (C) composition and (D) composition.Specifically, relative to the mass parts of hydraulic powder 100, the hydraulicity of the invention is preferably mixed Composition with more than the mass parts of dispersant composition 0.01, more preferably more than 0.05 mass parts, further preferred 0.1 mass parts with It is upper, still more preferably more than 0.15 mass parts, also, preferably below 5 mass parts, more preferably below 4 mass parts, it is further excellent Select below 3 mass parts, still more preferably below 2 mass parts.
The mixing of hydraulic powder, water, (A) composition, (B) composition and (C) composition can use mortar mixer, force The mixers such as two axle mixers are carried out.Additionally, it is preferred that mix more than 1 minute, more preferably mix more than 2 minutes, also, preferably Mixing less than 5 minutes, more preferably mix less than 3 minutes.On the preparation of hydraulic-composition, hydraulic-composition can be used The middle material illustrated, medicament and their amount.
The hydraulic-composition that hydraulic-composition is further filled into template and is conserved, made gained is solidified.Make For template, template, template of concrete product of building etc. can be enumerated.As filling to template method, can enumerate from Method that mixer is directly put into, with pump by hydraulic-composition force feed so as to importing method of template etc..
During the maintenance of hydraulic-composition, its solidification can be promoted in order to promote solidification to carry out heating curing.Here, add Thermal curing can keep hydraulic-composition so as to promote to solidify more than 40 DEG C and at less than 80 DEG C of temperature.
According to the present invention, there is provided a kind of manufacture method of firming body, it has following process：
Hydraulic powder, water, (A) composition, (B) composition, (C) composition are mixed so as to prepare the work of hydraulic-composition Sequence,
By the hydraulic-composition of preparation fill to template and conserved, make its solidify process, and
The process that the hydraulic-composition after solidification is stripped.
Dispersant for hydraulic composition composition, hydraulic-composition, the dispersant for hydraulic composition of the present invention Item described in the manufacture method of composition and the manufacture method of hydraulic-composition is readily applicable to the system of the firming body Make method.
As the firming body of the hydraulic-composition of the template using concrete product, in civil engineering product, can lift Go out in various concrete block products, box closed conduit product, tunnel fortification of shore protection etc. segmentation product, the horizontal stroke of bridge pier used Beam product etc., in product for building, can enumerate for curtain wall product, post, beam, floor building element product etc..
(the raising method of dispersive property)
The present invention is provided when mixing hydraulic powder, water, (A) composition and (B) so as to prepare hydraulic-composition, is added The raising method of dispersive property that add (C) composition, hydraulic powder for (A) composition He (B) composition.(A) composition and (B) Composition is widely known by the people respectively as the dispersant of hydraulic powder, by its dispersive property and the mobility of hydraulic-composition Improve.But even and if do not improved not only, flowed on the contrary with (A) composition and (B) composition, the mobility of hydraulic-composition Property significantly reduces.In the present invention, by adding (C) composition, though compared to and used the situation of (A) composition and (B) composition, The mobility of hydraulic-composition also improves.I.e., it is possible to say by adding (C) composition, make and used (A) composition and (B) composition Dispersant, for hydraulic powder dispersive property improve.
(A) composition used in the raising method of the dispersive property of the present invention, (B) composition and (C) composition concrete example and Preferred embodiment is identical with described in the dispersant for hydraulic composition composition of the present invention respectively.
In addition, concrete example and the side of being preferable to carry out of hydraulic powder used in the raising method of the dispersive property of the present invention Formula is identical with described in the hydraulic-composition of the present invention.
Divide in addition, the dispersant for hydraulic composition composition of the present invention, hydraulic-composition, hydraulic-composition are used Item described in the manufacture method of powder composite and the manufacture method of hydraulic-composition can be suitably employed in the present invention Dispersive property raising method in.
In addition to that mentioned above, the invention discloses composition, the conduct containing (A) composition, (B) composition and (C) composition The purposes of dispersant for hydraulic composition.
In addition, the invention discloses the composition containing hydraulic powder, water, (A) composition, (B) composition and (C) composition , purposes as hydraulic-composition.
For these purposes, the dispersant for hydraulic composition composition, inorganic of the present invention can be compatibly applicable Powder dispersant composition, hydraulic-composition, the manufacture method of dispersant for hydraulic composition composition, hydraulicity group Item described in the manufacture method of compound and the raising method of dispersive property.
In addition, the invention discloses for dispersant for hydraulic composition, contain (A) composition, (B) composition and (C) The composition of composition.
In addition, the invention discloses for hydraulic-composition, contain hydraulic powder, water, (A) composition, (B) composition The composition of (C) composition.
For these compositions, dispersant for hydraulic composition composition, the nothing of the present invention can be compatibly applicable Machine powder dispersant composition, hydraulic-composition, the manufacture method of dispersant for hydraulic composition composition, the hydraulicity Item described in the manufacture method of composition and the raising method of dispersive property.
＜ embodiments of the present invention ＞
Hereinafter, example goes out embodiments of the present invention., can be suitably using the hydraulicity of the present invention in these embodiments Composition dispersant composition, hydraulic-composition, the manufacture method of dispersant for hydraulic composition composition, the hydraulicity The item described in the manufacture method of composition and the raising method of dispersive property.
The ＞ of ＜ 1
A kind of hydraulic-composition dispersant composition, it contains：(A) there is the macromolecule for wrapping naphthalene-ring containing monomeric unit Compound,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by.
【Chemical formula 8】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
The dispersant for hydraulic composition composition that the above-mentioned ＞ of ＜ 1 of the ＞ of ＜ 2 are recorded, wherein, (A) composition is naphthalene sulfonic acids first Aldehyde condensate or its salt.
The dispersant for hydraulic composition composition that the above-mentioned ＞ of ＜ 2 of the ＞ of ＜ 3 are recorded, wherein, the Weight-average molecular of (A) composition Amount is preferably less than 200,000, is more preferably less than 100,000, is more preferably less than 80,000, is still more preferably Less than 50,000, still more preferably it is less than 30,000.
The dispersant for hydraulic composition composition that the ＞ of the ＜ 4 above-mentioned ＞ of ＜ 2 or the ＞ of ＜ 3 are recorded, wherein, (A) composition Weight average molecular weight is preferably more than 1,000, is more preferably more than 3,000, is more preferably more than 4,000, is further excellent Elect more than 5,000 as.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 4 of the ＞ of ＜ 5 is recorded, wherein, In solid constituent, preferably comprise more than the mass % of (A) composition 1, more preferably more than 3 mass %, further preferred 5 mass % with On, also, preferably below 99 mass %, more preferably below 97 mass %, further preferred below 95 mass %.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 5 of the ＞ of ＜ 6 is recorded, wherein, (B) carboxylic acid group of composition is-COOM0(M0Represent counter ion counterionsl gegenions) represented by group.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 6 of the ＞ of ＜ 7 is recorded, wherein, (B) phosphate of composition is-OPO (OM1)(OM2)(M1、M2It is identical or different, counter ion counterionsl gegenions are represented respectively.) represented by base Group.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 7 of the ＞ of ＜ 8 is recorded, wherein, (B) composition is selected from the phosphate with unsaturated bond and/or carboxylic acid compound and with containing the alkylene for possessing unsaturated bond The addition polymer of the compound of the monomeric unit of epoxide, contain the monomer list with the group in carboxylic acid group and phosphate Member and more than a kind of compound in the compound of monomeric unit and the condensation product of formaldehyde with alkylene oxide group.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 8 of the ＞ of ＜ 9 is recorded, wherein, (B) composition is to be selected from
(1) by alkoxy polyalkyleneglycol list (methyl) acrylate with being selected from (methyl) acrylic acid, can have hydroxyl The carbon number more than 1 of base and less than 3 (methyl) acrylate and with unsaturated group phosphate in more than a kind be copolymerized be total to Polymers, and
(2) ether compound of PAG and unsaturated alcohol and more than a kind in dicarboxylic acids and dicarboxylic anhydride Copolymer in the copolymer being copolymerized,
Here, (methyl) acrylate is acrylate or methacrylate, and (methyl) acrylic acid is acrylic acid or first Base acrylic acid.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 9 of the ＞ of ＜ 10 is recorded, wherein, (B) monomeric unit with carboxylic acid group of composition be derived from selected from the unsaturated bond that can carry out addition polymerization monocarboxylic acid with The monomeric unit of more than a kind of monomer in dicarboxylic acids with the unsaturated bond that can carry out addition polymerization, it is preferably to come from choosing From the list of more than a kind of monomer in acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid Body unit, it is more preferably the monomeric unit for coming from more than a kind of the monomer in methacrylic acid and acrylic acid.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 10 of the ＞ of ＜ 11 is recorded, wherein, (B) monomeric unit with phosphate of composition is derived from being selected from the phosphoric acid chemical combination with the unsaturated bond that can carry out addition polymerization Thing and the monomeric unit with more than a kind of monomer in the phosphate cpd for the aromatic functional groups that can carry out condensation polymerization, Preferably come from selected from di(2-ethylhexyl)phosphate ((2- hydroxyethyls) methacrylic acid) ester, di(2-ethylhexyl)phosphate ((2- hydroxyethyls) acrylic acid) ester, Mono phosphoric acid ester (2- hydroxyethyls) methacrylate, mono phosphoric acid ester (2- hydroxyethyls) acrylate, polyalkylene glycol mono (first Base) more than a kind of monomer in acrylate acid phosphoric acid ester and phenoxetol phosphate monomeric unit, more preferably Come from and be selected from di(2-ethylhexyl)phosphate ((2- hydroxyethyls) methacrylic acid) ester, mono phosphoric acid ester (2- hydroxyethyls) methacrylate and benzene The monomeric unit of more than a kind of monomer in ethoxy-ethanol phosphate.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 11 of the ＞ of ＜ 12 is recorded, wherein, (B) monomeric unit with alkylene oxide group of composition is derived from the unsaturated bond and alkylene oxide group that can carry out addition polymerization The monomeric unit of compound, preferably come from selected from alkoxy polyalkyleneglycol list (methyl) acrylate and polyalkylene The monomeric unit of more than a kind of monomer in the ether compound of glycol and unsaturated alcohol.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 12 of the ＞ of ＜ 13 is recorded, wherein, (B) monomeric unit with alkylene oxide group of composition is derived from selected from methoxy poly (ethylene glycol), the poly- Asia third of the poly- ethylidene of methoxyl group The poly- ethylidene polytrimethylene glycol of base glycol, ethyoxyl polyethylene glycol, ethyoxyl, propoxyl group polyethylene glycol, propoxyl group gather sub- second Carboxylate, the allyl of the single end alkyl end-blocking PAG and acrylic or methacrylic acid of base polytrimethylene glycol etc. The addition of the oxirane of base alcohol and/or the addition product of expoxy propane, the oxirane of isoprene alcohol and/or expoxy propane Thing, the addition product of the oxirane of vinyl alcohol and/or expoxy propane, the oxirane of acrylic acid and/or expoxy propane plus Into the monomeric unit of the monomer in the addition product of the oxirane and/or expoxy propane of thing and methacrylic acid.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 13 of the ＞ of ＜ 14 is recorded, wherein, (B) the average addition molal quantity of the alkylene oxide group of monomeric unit, each monomeric unit with alkylene oxide group of composition is excellent Elect more than 5 as, more preferably more than 7, more preferably more than 20, also, preferably less than 150, more preferably 130 with Under.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 14 of the ＞ of ＜ 15 is recorded, wherein, (B) monomeric unit with alkylene oxide group of composition is derived from the monomeric unit of the monomer represented by following formulas (B1).
【Chemical formula 9】
(in formula, R1bRepresent hydrogen atom or methyl.AO represents the alkylene oxide group of carbon number 2 or 3, and n is AO average addition mole Number, represent more than 5 and less than 150 number.Z represents ether (- O-) or ester group (- COO-).R2bRepresent hydrogen atom or carbon number more than 1 And less than 3 alkyl.〕
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 15 of the ＞ of ＜ 16 is recorded, wherein, (B) composition is selected from the polymer comprising the monomeric unit with carboxylic acid group and comprising monomeric unit and tool with carboxylic acid group There is the polymer in the polymer of the monomeric unit of phosphate.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 16 of the ＞ of ＜ 17 is recorded, wherein, (B) composition is more than a kind of polymer being selected from following (b1), (b2) and (b3).
(b1) polymer of methacrylic acid and methoxy poly (ethylene glycol) monomethacrylates as composition monomer is included, Preferably as composition monomer and first in monomer is formed comprising methacrylic acid and methoxy poly (ethylene glycol) monomethacrylates Base acrylic acid is 40 moles of more than % and 90 mole of below %, methoxy poly (ethylene glycol) monomethacrylates are in composition monomer 10 moles of more than % and 60 mole of below %, the polymer that weight average molecular weight is less than more than 10,000 100,000；
(b2) formaldehyde condensation products of polyoxyethylene list phenyl ether and phenoxetol phosphate as composition monomer are included, Preferably as the formaldehyde condensation products for forming monomer and formed comprising polyoxyethylene list phenyl ether and phenoxetol phosphate Polyoxyethylene list phenyl ether is 10 moles of more than % and 70 mole of below %, forms phenoxetol phosphoric acid in monomer in monomer Ester is 30 moles of more than % and 90 mole of below %, the formaldehyde condensation products that weight average molecular weight is less than more than 5,000 10,0000；
(b3) preferably included as the polymer for forming monomer comprising methacrylic acid and 2- hydroxyethylmethacry,ates Methacrylic acid and 2- hydroxyethylmethacry,ates as form monomer and form methacrylic acid in monomer be 45 moles of % with Upper and 95 moles of below %, form 2- hydroxyethylmethacry,ates in monomer be 5 moles of more than % and 55 mole of below %, weight it is equal Molecular weight is less than more than 5,000 100,000 polymer.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 17 of the ＞ of ＜ 18 is recorded, wherein, (B) weight average molecular weight of composition is preferably 5, more than 000, more preferably 10, more than 000, more preferably 30, more than 000, Preferably less than 500,000, it is more preferably less than 150,000, is still more preferably less than 100,000.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 18 of the ＞ of ＜ 19 is recorded, wherein, Preferably comprised in solid constituent more than the mass % of (B) composition 1, more preferably more than 3 mass %, further preferred more than 5 mass %, Also, it is preferred that below 95 mass %, more preferably below 90 mass %, further preferred below 80 mass %.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 19 of the ＞ of ＜ 20 is recorded, wherein, (A) composition is preferably more than 0.01 in terms of (A)/(B), is more preferably more than 0.05, further preferably with the mass ratio of (B) composition For more than 0.1, be still more preferably more than 0.3, be still more preferably more than 1.0, be still more preferably more than 3.0, Also, preferably less than 100, be more preferably less than 55, more preferably less than 10, still more preferably be less than 5.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 20 of the ＞ of ＜ 21 is recorded, wherein, By the R in formula (C1)11As R11The HLB of-H compound is preferably less than 3.21, is more preferably less than 1.31, further Preferably below -0.59, also, it is preferably more than -3.46, more preferably more than -2.51, more preferably more than -1.56.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 21 of the ＞ of ＜ 22 is recorded, wherein, By the R in formula (C2)21As R21- H compound, by the R in formula (C3)31As R31- H compound and by formula (C4) R in41As R41- H compound HLB difference identical or differently be preferably less than 3.21, be more preferably 1.31 with Under, also, be preferably more than -3.46, more preferably more than -2.51, more preferably more than -1.56, still more preferably To be more than -0.60.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 22 of the ＞ of ＜ 23 is recorded, wherein, R in formula (C1)11, R in formula (C2)21, R in formula (C3)31And the R in formula (C4)41It is respectively identical or not Same (hereinafter referred to as substitutes virtue selected from alkyl, alkenyl, aralkyl, aryl and the alkyl in the aryl with substituent Base) in group, the group being preferably selected from alkyl, alkenyl and substituted aryl.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 23 of the ＞ of ＜ 24 is recorded, wherein, R in formula (C1)11Carbon number be preferably more than 8, more preferably more than 12, more preferably more than 16, also, be preferably Less than 22, less than 20, more preferably less than 18 are more preferably.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 24 of the ＞ of ＜ 25 is recorded, wherein, R in formula (C2)21Carbon number be preferably more than 8, more preferably more than 12, more preferably more than 16, also, be preferably Less than 22, less than 20, more preferably less than 18 are more preferably.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 25 of the ＞ of ＜ 26 is recorded, wherein, R in formula (C3)31Carbon number be preferably more than 8, more preferably more than 12, more preferably more than 16, also, be preferably Less than 22, less than 20, more preferably less than 18 are more preferably.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 26 of the ＞ of ＜ 27 is recorded, wherein, R in formula (C4)41Carbon number be preferably more than 8, more preferably more than 12, more preferably more than 16, also, be preferably Less than 22, less than 20, more preferably less than 18 are more preferably.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 27 of the ＞ of ＜ 28 is recorded, wherein, R in formula (C1)11, R in formula (C2)21, R in formula (C3)31And the R in formula (C4)41It is respectively identical or not Alkyl or alkenyl together, preferably aliphatic alkyl or aliphatic alkenyl, it is more preferably straight-chain aliphatic alkyl or straight chain fatty Race's alkenyl, more preferably straight chain Primary Fatty race's alkyl or straight chain Primary Fatty race alkenyl.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 28 of the ＞ of ＜ 29 is recorded, wherein, R in formula (C1)11And the R in formula (C2)21It is preferably more than 10, further for the identical or different carbon number that is respectively selected from Preferably more than 12, also, preferably less than 22, more preferably less than 20 alkyl or alkenyl and the alkyl or the alkene Group in the group that the hydrogen atom of base is substituted with a substituent, and the phenyl of alkyl substitution.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 29 of the ＞ of ＜ 30 is recorded, wherein, R in formula (C1)11And the R in formula (C2)21It is respectively selected from for identical or different
Carbon number is preferably more than 10, more preferably more than 12, also, preferably less than 22, more preferably 20 Following alkyl, it is preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, more preferably straight chain Primary Fatty race Alkyl,
Carbon number is preferably more than 10, more preferably more than 12, also, preferably less than 22, more preferably 20 Following alkenyl, it is preferably aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl, more preferably straight chain Primary Fatty race Alkenyl,
Carbon number is preferably more than 1, more preferably more than 2, also, preferably less than 10, more preferably less than 8 Alkyl-substituted phenyl,
The phenyl of benzyl substitution, and
Group in the phenyl of styrol.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 30 of the ＞ of ＜ 31 is recorded, wherein, R in formula (C1)11, R in formula (C2)21, R in formula (C3)31And the R in formula (C4)41To be identical or different It is respectively selected from decyl, lauryl, myristyl, palmityl, stearyl, behenyl base, iso stearyl, oil base, tribenzyl phenyl, two Alkyl in styrenated phenyl and tristyrenated phenyl, it is preferably selected from lauryl, myristyl, palmityl, tristearin Alkyl in base, behenyl base, iso stearyl, oil base, tribenzyl phenyl and distyrenated phenyl, more preferably selected from bay Alkyl in base, myristyl, palmityl, stearyl, oil base, tribenzyl phenyl and distyrenated phenyl.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 31 of the ＞ of ＜ 32 is recorded, wherein, X in formula (C1) is O.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 32 of the ＞ of ＜ 33 is recorded, wherein, X in formula (C2) is O.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 33 of the ＞ of ＜ 34 is recorded, wherein, R in formula (C2)22For hydrogen atom.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 34 of the ＞ of ＜ 35 is recorded, wherein, AO in formula (C1), formula (C2), formula (C3) and formula (C4) includes the alkylene of carbon number 2 or 3 respectively identical or differently The alkylene oxide group of epoxide or carbon number 2.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 35 of the ＞ of ＜ 36 is recorded, wherein, N1 in formula (C1) is preferably more than 1, is more preferably more than 10, is more preferably more than 20, is still more preferably 30 More than, still more preferably for more than 40, be still more preferably more than 50 number, and preferably less than 200, more preferably Less than 150, more preferably less than 100 number.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 36 of the ＞ of ＜ 37 is recorded, wherein, N2 in formula (C2) is preferably more than 5, more preferably more than 9, more preferably more than 12, still more preferably for 20 with Number that is upper, being still more preferably more than 28, and preferably less than 200, more preferably less than 150, more preferably 100 Below, it is still more preferably less than 60, is still more preferably less than 35 number.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 37 of the ＞ of ＜ 38 is recorded, wherein, N3's and n4 in formula (C3) adds up to more than 1, is preferably more than 20, more preferably more than 50 number, also, for 300 with Under, be preferably less than 200, more preferably less than 150, more preferably less than 100 number.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 38 of the ＞ of ＜ 39 is recorded, wherein, N5's and n6 in formula (C4) adds up to more than 1, is preferably more than 20, more preferably more than 50 number, also, for 300 with Under, be preferably less than 200, more preferably less than 150, more preferably less than 100 number.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 39 of the ＞ of ＜ 40 is recorded, wherein, (C) composition is more than a kind of the compound in (C1) and (C4).
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 40 of the ＞ of ＜ 41 is recorded, wherein, (C) composition is more than a kind of the compound in (C3) and (C4).
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 41 of the ＞ of ＜ 42 is recorded, wherein, (C) composition is more than a kind of the compound in (C1) and (C3).
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 42 of the ＞ of ＜ 43 is recorded, wherein, Preferably comprised in solid constituent more than the mass % of (C) composition 2, more preferably more than 5 mass %, further preferred more than 7 mass %, Also, it is preferred that below 90 mass %, more preferably below 80 mass %, further preferred below 70 mass %.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 43 of the ＞ of ＜ 44 is recorded, wherein, (A) the total and mass ratio of (C) composition of composition and (B) composition by (C)/((A)+(B)) in terms of preferably more than 0.01, more preferably For more than 0.02, more preferably more than 0.05, be still more preferably more than 0.1, be still more preferably more than 0.3, Still more preferably for more than 0.4, be still more preferably more than 0.6, also, preferably less than 10, more preferably less than 7, More preferably less than 5, still more preferably for less than 4, be still more preferably less than 2, be still more preferably 1 with Under, still more preferably be less than 0.8.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 44 of the ＞ of ＜ 45 is recorded, wherein, (D) defoamer (hereinafter referred to as (D) composition) preferably comprises fatty acid ester system defoamer.
The dispersant for hydraulic composition composition that the above-mentioned ＞ of ＜ 45 of the ＞ of ＜ 46 are recorded, wherein, in solid constituent preferably Containing more than the mass % of (D) composition 0.001, more preferably more than 0.01 mass %, further preferred more than 0.1 mass %, also, It is preferred that below 10 mass %, more preferably below 5 mass %, further preferred below 1 mass %.
The dispersant for hydraulic composition composition that the ＞ of the ＜ 47 above-mentioned ＞ of ＜ 45 or the ＞ of ＜ 46 are recorded, wherein, (C) composition Mass ratio with (D) composition is preferably more than 0.00001 in terms of (D)/(C), is more preferably more than 0.00005, further preferably For more than 0.0001, also, preferably less than 0.5, more preferably less than 0.1, more preferably less than 0.05.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 47 of the ＞ of ＜ 48 is recorded, wherein, Dispersant for hydraulic composition composition contains water, and the content of water be preferably in the composition more than 10 mass %, More preferably more than 30 mass %, more preferably more than 50 mass %, also, preferably below 90 mass %, more preferably For below 70 mass %.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 48 of the ＞ of ＜ 49 is recorded, wherein, Dispersant for hydraulic composition composition contains water, and the content of (A) composition be preferably 1 mass % in the composition with Upper, more preferably more than 4 mass %, more preferably more than 7 amount %, also, preferably below 50 mass %, be more preferably Below 32 mass %, more preferably below 27 mass %.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 49 of the ＞ of ＜ 50 is recorded, wherein, Dispersant for hydraulic composition composition contains water, and the content of (B) composition be preferably 1 mass % in the composition with Upper, more preferably more than 4 mass %, more preferably more than 7 mass %, also, preferably below 60 mass %, more preferably For below 50 mass %, more preferably below 32 mass %.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 50 of the ＞ of ＜ 51 is recorded, wherein, Dispersant for hydraulic composition composition contains water, and the content of (C) composition be preferably 1 mass % in the composition with Upper, more preferably more than 4 mass %, more preferably more than 7 mass %, also, preferably below 60 mass %, more preferably For below 50 mass %, more preferably below 32 mass %.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 51 of the ＞ of ＜ 52 is recorded, wherein, Dispersant for hydraulic composition composition contains water, and total content of (A) composition, (B) composition and (C) composition is at this It is preferably more than 10 mass %, more preferably more than 20 mass % in composition, is more preferably more than 30 mass %, and And preferably below 90 mass %, more preferably below 70 mass %, more preferably below 50 mass %.
The ＞ of ＜ 53
A kind of hydraulic-composition, contains：
Hydraulic powder,
Water,
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by.
【Chemical formula 10】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
The hydraulic-composition that the above-mentioned ＞ of ＜ 53 of the ＞ of ＜ 54 are recorded, wherein, (A) composition be naphthalene sulfonic acid-formaldehyde condensation product or its Salt.
The hydraulic-composition that the ＞ of the ＜ 55 above-mentioned ＞ of ＜ 53 or the ＞ of ＜ 54 are recorded, wherein, the weight average molecular weight of (A) composition is excellent Elect less than 200,000 as, more preferably less than 100,000, more preferably less than 80,000, be still more preferably 50, Less than 000, still more preferably it is less than 20,000.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 55 of the ＞ of ＜ 56 is recorded, wherein, the weight of (A) composition is equal Molecular weight is preferably more than 1,000, is more preferably more than 3,000, is more preferably more than 4,000, is still more preferably More than 5,000.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 56 of the ＞ of ＜ 57 is recorded, wherein, the weight of (A) composition is equal Molecular weight is preferably less than 200,000, is more preferably less than 100,000, is more preferably less than 80,000, is further excellent Elect 50, less than 000 as, be still more preferably 20, less than 000, also, preferably 1, more than 000, more preferably 3,000 with Above, it is more preferably more than 4,000, is still more preferably more than 5,000.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 57 of the ＞ of ＜ 58 is recorded, wherein, hydraulic powder is Cement or gypsum.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 58 of the ＞ of ＜ 59 is recorded, wherein, water/hydraulic powder Than being preferably more than 15 mass %, more preferably more than 20 mass %, also, preferably below 50 mass %, more preferably 45 Below quality %, more preferably below 40 mass %.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 59 of the ＞ of ＜ 60 is recorded, wherein, relative to the hydraulicity The mass parts of powder 100, preferably comprise more than the mass parts of (A) composition 0.01, more preferably more than 0.03 mass parts, further preferably More than 0.05 mass parts, still more preferably more than 0.1 mass parts, still more preferably more than 0.15 mass parts, further It is preferred that more than 0.30 mass parts, also, preferably below 2 mass parts, more preferably below 1.5 mass parts, further preferred 1.0 mass Below part, still more preferably below 0.80 mass parts.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 60 of the ＞ of ＜ 61 is recorded, wherein, relative to the hydraulicity The mass parts of powder 100, preferably comprise more than the mass parts of (B) composition 0.005, more preferably more than 0.03 mass parts, further preferably More than 0.05 mass parts, still more preferably more than 0.1 mass parts, still more preferably more than 0.15 mass parts, further It is preferred that more than 0.2 mass parts, also, preferably below 3 mass parts, more preferably below 2 mass parts, further preferred 1.5 mass parts Below, still more preferably below 1.0 mass parts, still more preferably below 0.7 mass parts, still more preferably 0.5 mass Below part.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 61 of the ＞ of ＜ 62 is recorded, wherein, relative to the hydraulicity The mass parts of powder 100, preferably comprise more than the mass parts of (C) composition 0.01, more preferably more than 0.02 mass parts, further preferably More than 0.04 mass parts, still more preferably more than 0.06 mass parts, still more preferably more than 0.08 mass parts, further It is preferred that more than 0.1 mass parts, still more preferably more than 0.3 mass parts, also, preferably below 2 mass parts, more preferably 1.5 matter Measure part below, below further preferred 1.3 mass parts, still more preferably below 1 mass parts, still more preferably 0.8 mass Below part, still more preferably below 0.6 mass parts.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 62 of the ＞ of ＜ 63 is recorded, wherein, relative to the hydraulicity The mass parts of powder 100, preferably comprise more than total 0.005 mass parts of (A) composition and (B) composition, more preferably 0.03 mass parts More than, more than further preferred 0.1 mass parts, still more preferably more than 0.15 mass parts, still more preferably 0.3 mass parts More than, also, preferably below 5 mass parts, more preferably below 3 mass parts, below further preferred 2 mass parts, further it is excellent Select below 1 mass parts.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 63 of the ＞ of ＜ 64 is recorded, wherein, relative to the hydraulicity The mass parts of powder 100, are preferably comprised more than total 0.01 mass parts of (A) composition, (B) composition and (C) composition, more preferably 0.05 It is more than mass parts, more than further preferred 0.1 mass parts, still more preferably more than 0.14 mass parts, still more preferably More than 0.20 mass parts, still more preferably more than 0.40 mass parts, still more preferably more than 0.70 mass parts, also, excellent Select below 5 mass parts, more preferably below 4 mass parts, below further preferred 3 mass parts, still more preferably 2 mass parts with Under, still more preferably below 1.5 mass parts.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 64 of the ＞ of ＜ 65 is recorded, wherein, (A) composition and (B) The mass ratio of composition is preferably more than 0.01 in terms of (A)/(B), is more preferably more than 0.05, is more preferably more than 0.1, more More preferably more than 0.3, it is still more preferably more than 1.0, is still more preferably more than 3.0, also, is preferably Less than 100, be more preferably less than 55, more preferably less than 10, still more preferably be less than 5.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 65 of the ＞ of ＜ 66 is recorded, wherein, (A) composition and (B) The mass ratio of total and (C) composition of composition is preferably more than 0.01 by (C)/((A)+(B)) in terms of, be more preferably more than 0.02, More preferably more than 0.05, it is still more preferably more than 0.1, is still more preferably more than 0.3, still more preferably For more than 0.4, be still more preferably more than 0.6, also, preferably less than 10, more preferably less than 7, more preferably 5 Below, it is still more preferably less than 4, be still more preferably less than 2, is still more preferably less than 1, still more preferably For less than 0.8.
The hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 66 of the ＞ of ＜ 67 is recorded, wherein, also defoamed containing (D) Agent (hereinafter referred to as (D) composition), preferred fat acid esters system defoamer.
The hydraulic-composition that the above-mentioned ＞ of ＜ 67 of the ＞ of ＜ 68 are recorded, wherein, it is excellent relative to the mass parts of hydraulic powder 100 Choosing contains more than the mass parts of (D) composition 0.00005, more preferably more than 0.00025 mass parts, further preferred 0.0005 mass parts More than, also, preferably below 0.1 mass parts, more preferably below 0.075 mass parts, below further preferred 0.05 mass parts.
The hydraulic-composition that the ＞ of the ＜ 69 above-mentioned ＞ of ＜ 67 or the ＞ of ＜ 68 are recorded, wherein, the matter of (C) composition and (D) composition Amount ratio is preferably more than 0.00001, more preferably more than 0.00005, more preferably more than 0.0001 in terms of (D)/(C), Also, preferably less than 0.5, it is more preferably less than 0.1, more preferably less than 0.05.
The ＞ of ＜ 70
A kind of manufacture method of dispersant for hydraulic composition composition, it is will
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound mixing in the compound represented by compound and following formulas (C4) represented by
Dispersant for hydraulic composition composition manufacture method.
【Chemical formula 11】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
The ＞ of ＜ 71
A kind of manufacture method of hydraulic-composition, it is will
Hydraulic powder,
Water,
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound mixing in the compound represented by compound and following formulas (C4) represented by
Hydraulic-composition manufacture method.
【Chemical formula 12】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
The ＞ of ＜ 72
By hydraulic powder, water, (A) has the high-molecular compound for wrapping naphthalene-ring containing monomeric unit, and (B), which contains, has choosing It is changed into the group of carboxylic acid group from carboxylic acid group, phosphate, by hydrolysis and by hydrolyzing the base being changed into the group of phosphate The monomeric unit of group, monomeric unit, weight average molecular weight more than 1,000 and less than 1,000,000 with having alkylene oxide group When mixed with polymers is so as to prepare hydraulic-composition,
Add (C) and be selected from compound represented by following formulas (C1), the compound represented by following formulas (C2), following More than a kind in the compound represented by compound and following formulas (C4) represented by formula (C3) it is compound, for (A) and the dispersive property of the hydraulic powder of (B) raising method.
【Chemical formula 13】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
Dispersant for hydraulic composition composition, the work that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 52 of the ＞ of ＜ 73 is recorded For dispersant for hydraulic composition and then as the use of the dispersant comprising hydraulic powder and the hydraulic-composition of water On the way.
The dispersant for hydraulic composition composition that any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 52 of the ＞ of ＜ 74 is recorded, it is used In dispersant for hydraulic composition and then the dispersant of hydraulic-composition comprising hydraulic powder and water.
Use composition, as hydraulic-composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 69 of the ＞ of ＜ 75 is recorded On the way.
The composition that any one of the above-mentioned ＞ of 53 ＞ of ＜~＜ 69 of the ＞ of ＜ 76 is recorded, it is used for hydraulic-composition.
The ＞ of ＜ 77
A kind of inorganic particle dispersant composition, contains：
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolyze change For the monomeric unit of the group in the group of phosphate, with the monomeric unit of alkylene oxide group, weight average molecular weight 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) more than a kind of the compound in the compound represented by compound and following formulas (C4) represented by.
【Chemical formula 14】
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
(in formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression 1 Above and less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be 1 with It is upper and less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.〕
Embodiment
<Embodiment 1 and comparative example 1>
(1) preparation of mortar
Use mortar mixer (the omnipotent mixing and blending machine model of Co., Ltd.'s Dalton Plan：5DM-03- γ), put into cement (C), thin aggregate (S) and using mortar mixer low speed rotation (63rpm) carry out 10 seconds be kneaded, add comprising (A) composition, (B) mixing water (W) of composition, (C) composition and defoamer.Also, carried out using the low speed rotation (63rpm) of mortar mixer Formal mixing in 120 seconds, so as to the mortar that preparation temperature is 22 DEG C or 33 DEG C.The mortar that 22 DEG C of temperature is in 22 DEG C of (stirrings of room temperature The temperature of machine be 22 DEG C) under, used cement, thin aggregate and water temperature be 22 DEG C raw material and prepare.Temperature is 33 DEG C Mortar be in 33 DEG C of thermostatic chamber, the temperature using mixer, cement, thin aggregate and water is 33 DEG C of mixer and raw material And prepare.
On the matching requirements of mortar, the mortar of arbitrary temp is cement 400g, thin aggregate 700g, and water/cement ratio (W/C) 35 mass % are set to.
The composition used is following material.It should be noted that on the compound with ethyleneoxy group, with bracket Numeral represent the average addition molal quantity of oxirane (other embodiments and comparative example are also set to identical).(C) POE of composition It is the abbreviation of polyoxyethylene, the numeral in bracket is oxirane average addition molal quantity (other embodiments and comparative example Also it is set to identical).
Water (W)：Running water is used.
Cement (C)：Portland cement (two kinds of mixing：Pacific Ocean cement/Sumitomo Osaka cement=1/1, quality Than) density 3.16g/cm3
Thin aggregate (S)：Produce mountain sand density 2.55g/cm in Chengyang3
(A) composition：The sodium salt of naphthalene sulfonic acid-formaldehyde condensation product, weight average molecular weight 15,000
(B) composition：Sodium salt of methacrylic acid/methoxy poly (ethylene glycol) (23) monomethacrylates copolymer (mole Than 70/30, weight average molecular weight 50000)
(C) composition：POE (26) oleyl ether (R in formula (C2)21For oil base, R22It is sub- for hydrogen atom, X O, AO Ethyl epoxide, n2For 26 compound, as R21The HLB of-H compound is -1.55.〕
Defoamer：FOAMLEX 797 (fatty acid ester system defoamer), Nicca Chemical Co., Ltd's system, to above-mentioned mortar 0.05g is added in cooperation.
(2) evaluation of mobility
According to JIS R 5201 test method, the flowing of the mortar of preparation is determined.However, without assigning motion of dropping Operation.The measure flowed to the mortar that temperature is 22 DEG C or 33 DEG C.Show the result in table 1,2.
[table 1]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2-in-1 meter addition：Add relative to (A) composition of the mass parts of cement 100, (B) composition and the total of (C) composition Dosage (mass parts)
* 3 addition ratios：Relative value (the matter of addition when necessary addition at 22 DEG C to be set to 100 mass % Measure %)
From comparative example 1-1, for (A) composition, when 22 DEG C of mortar temperature compared with, during 33 DEG C of mortar temperature in order to Addition necessary to obtaining defined mobility (200mm) is reduced.
From comparative example 1-2, for (B) composition, when 22 DEG C of mortar temperature compared with, during 33 DEG C of mortar temperature in order to Addition increase necessary to mobility as defined in obtaining.
But from comparative example 1-3,1-4, simple and in the case of having used (A) composition and (B) composition, mortar temperature The mobility of mortar is greatly reduced at 22 DEG C, cannot defined mobility.
On the other hand, it is combined with the embodiment 1-1 of (A) composition, (B) composition and (C) composition, 22 DEG C of mortar temperature and 33 The reduction of mobility does not occur at DEG C, in addition, roughly the same in order to obtain addition necessary to defined mobility.
It should be noted that, although not shown in table, but in comparative example 1-3,1-4 at 33 DEG C of mortar temperature ash The mobility of slurry is also greatly reduced, cannot defined mobility.
[table 2]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2-in-1 meter addition：Relative to total addition of the mass parts of cement 100 (A) composition, (B) composition and (C) composition Measure (mass parts)
* 3 mortar flows ratios：The relative value (%) of mortar flows when mortar flows at 22 DEG C are set into 100%
From comparative example 1-5, (A) composition is under identical addition, compared with 22 DEG C of mortar temperature, mortar temperature 33 DEG C when mortar flows increase.
From comparative example 1-6, (B) composition is under identical addition, compared with 22 DEG C of mortar temperature, mortar temperature 33 DEG C when mortar flows reduce.
On the other hand, it is known that be combined with the embodiment 1-2 of (A) composition, (B) composition and (C) composition, added in identical Under amount, substantially equal mobility is shown at 22 DEG C and 33 DEG C of mortar temperature.
It should be noted that by (A) composition of the embodiment 1-2 in the embodiment 1-1 or table 2 in corresponding to table 1, (B) composition can obtain the dispersant for hydraulic composition composition of the present invention with mixing water in (C) composition.Now, hydraulic Property composition dispersant composition contains (A) composition, (B) composition, (C) composition and water.(A) composition in said composition contains Amount can be set to 20~40 mass %.Use (B) composition and (C) composition of the mass ratio of (A) composition corresponding to the amount.With group The generally 100 mass % amount of compound uses water.The stability of the composition of such 1 liquid type is good, and if (A) composition, (B) composition and (C) composition are identical with table 1 relative to the addition of cement, with regard to that can obtain good mortar flows.
<Embodiment 2 and comparative example 2>
Mortar is prepared same as Example 1ly, and evaluates mobility and the compressive strength of grout cures body.However, flowing Property for temperature be that 22 DEG C of mortar is evaluated.In addition, (C) composition has used POE (60) oleyl ether sulfuric ester compound ammonium salt. The compound for being somebody's turn to do (C) composition is the R in formula (C1)11Be ethyleneoxy group for oil base, X O, AO, n1 60, M be ammonium ion Compound, as R11The HLB of-H compound is -1.55.In addition, compressive strength (10 DEG C, after conserving in 18 hours air Compressive strength) evaluation carried out by Shimadzu Scisakusho Ltd's system, strength-testing machine CONCRETO 2000.As a result exist Shown in table 3.
[table 3]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2-in-1 meter addition：Add relative to (A) composition of the mass parts of cement 100, (B) composition and the total of (C) composition Dosage (mass parts)
From comparative example 2-1~2-2, the situation of dispersant is added in a manner of mortar flows are in 180~200mm Under, (A) composition and (B) composition are difficult to obtain compressive strength when each independent.
From comparative example 2-3, even if combination (A) composition and (B) composition, also cannot get good mortar flows, compress Intensity also terrifically reduces.
From embodiment 2-1, by combining (A) composition, (B) composition and (C) composition, good mortar stream can be obtained Dynamic, compressive strength also improves compared with the exclusive use of dispersant.
From comparative example 2-4~2-5, even in in (A) composition of embodiment 2-1 equivalent or (B) composition and with (C) Composition, it also cannot get good mortar flows.
From comparative example 2-6, if removing (C) composition from embodiment 2-1, it cannot get good mortar flows.
<Embodiment 3 and comparative example 3>
Mortar is prepared same as Example 1ly, and evaluates mobility.However, mobility is entered to the mortar that temperature is 22 DEG C Row evaluation.In addition, (C) composition has used the material of table 4,5.As a result it is shown in table 4,5.
[table 4]
[table 5]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2 R-H HLB：Equivalent to R11- H compound, equivalent to R21- H compound, equivalent to R31- H chemical combination Thing, equivalent to R41- H compound, vaccenic acid, the HLB obtained by Davis (Davies) method of propane or ethane
* 3 total additions：Relative to total addition of the mass parts of cement 100 (A) composition, (B) composition and (C) composition Measure (mass parts)
From comparative example 3-1~3-3, for (A) composition and (B) composition, by and with them, mortar flows are notable Reduce.It should be noted that, although not shown in table 4, but any reality of comparative example 3-1 and comparative example 3-2 compressive strength ratio It is all low to apply example.
From embodiment 3-1~3-43, by the addition of (C) composition, with and used the ratio of (A) composition and (B) composition Compared compared with example 3-3, mortar flows improve.
<Embodiment 4 and comparative example 4>
Mortar is prepared same as Example 1ly, and evaluates mobility.However, mobility is directed to the mortar that temperature is 22 DEG C Evaluated.In addition, (B) composition has used material as follows.In addition, (C) composition has used POE (60) oleyl ether sulfuric acid Carboxylate ammonium salt or POE (30) oleyl ether sulfuric ester compound ammonium salt.POE (60) oleyl ether sulfuric ester compound ammonium salt is formula (C1) In R11It is ethyleneoxy group, n1 60, the compound that M is ammonium ion for oil base, X O, AO, and is used as R11- H compound HLB be -1.55.In addition, POE (30) oleyl ether sulfuric ester compound ammonium salt is the R in formula (C1)11It is for oil base, X O, AO Ethyleneoxy group, n1 30, the compound that M is ammonium ion and it is used as R11The HLB of-H compound is -1.55.As a result in table 6 In show.
* (B) composition used
The manufacture method for the embodiment that B-1~B-4 referenced patents the 2274445th is manufactured.
·B-1：Sodium salt of methacrylic acid/methoxy poly (ethylene glycol) (9) monomethacrylates=60/40 (mol ratio) Copolymer (Mw50000)
·B-2：Sodium salt of methacrylic acid/methoxy poly (ethylene glycol) (23) monomethacrylates=70/30 (mol ratio) Copolymer (Mw50000)
·B-3：Sodium salt of methacrylic acid/methoxy poly (ethylene glycol) (120) monomethacrylates=85/15 (mol ratio) Copolymer (Mw70000)
·B-4：Phosphoric acid -2- (methacryloxy) ethyl ester/methoxy poly (ethylene glycol) (23) monomethacrylates= The copolymer (Mw40000) of 60/40 (mol ratio)
·B-5：With the side of the Japanese Unexamined Patent Application Publication paragraph 0050 " [preparation 2 of condensation polymer of the invention] " of No. 2008-517080 (oxirane) that method obtains, poly- single phenyl ether (2000g/ moles), phenoxetol phosphate (2- phenoxetol di(2-ethylhexyl)phosphates The mixture of hydrogen ester and 2- phenoxetol hydrogen phosphates) and formaldehyde condensation polymer (20000g/ moles)
[table 6]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2-in-1 meter addition：Add relative to (A) composition of the mass parts of cement 100, (B) composition and the total of (C) composition Dosage (mass parts)
From comparative example 4-6~4-10, for (A) composition and (B) composition, by and with them, mortar flows are bright It is aobvious to reduce.
From embodiment 4-1~4-5, by the addition of (C) composition, with and used the comparison of (A) composition and (B) composition Example 4-6~4-10 is compared, and mortar flows significantly improve.
The ＞ of ＜ comparative examples 5
Mortar is prepared same as Example 1ly, and evaluates mobility.But instead of (C) composition, calcium formate is added mixed Heshui (W) is so as to preparing mortar.In addition, mobility is evaluated for the mortar that temperature is 22 DEG C.As a result shown in table 7. In table 7, embodiment 2-1 and comparative example 2-1~2-6 result are also described in the lump.
[table 7]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2-in-1 meter addition：Relative to (A) composition, (B) composition and (C) composition or calcium formate of the mass parts of cement 100 Total addition (mass parts)
From comparative example 5-1,5-2, calcium formate can not be improved due to and with (A) composition and (B) composition and the ash that reduces Slurry flowing.
<Embodiment 6 and comparative example 6>
Mortar is prepared same as Example 1ly, and evaluates mobility.Wherein, (A) composition, (B) composition and (C) composition Addition is as shown in table 8.In addition, mobility is evaluated for the mortar that temperature is 22 DEG C.As a result shown in table 8.
[table 8]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2-in-1 meter addition：Add relative to (A) composition of the mass parts of cement 100, (B) composition and the total of (C) composition Dosage (mass parts)
From embodiment 6-1~6-5, even in different mass ratioes and having used the situation of (A) composition and (B) composition Under, mortar flows can also be improved by (C) composition.
<Embodiment 7 and comparative example 7>
Ground same as Example 1 preparation temperature is 22 DEG C of mortar, and evaluates mixing and start to the flowing after certain time Property.The initial stage of mixing is the time point that addition mixing water (W), cement initially contact with mixing water into mortar mixer.
As a result shown in table 10.
It should be noted that mortar coordinates as shown in table 9.Cement (C) used in mortar, thin aggregate (S), water (W), disappear Infusion is same as Example 1.
In addition, the addition of (A) composition, (B) composition and (C) composition is as shown in table 10.In addition, (A) composition, (B) into Divide and (C) composition has used following material.
(A) composition：The sodium salt of naphthalene sulfonic acid-formaldehyde condensation product, weight average molecular weight 15,000
(B) composition：2- hydroxyethylmethacry,ates/methoxy poly (ethylene glycol) (23) monomethacrylates copolymer (mol ratio 82/18, weight average molecular weight 2000)
(C) composition：POE (60) oleyl ether (R in formula (C2)21For oil base, R22It is sub- for hydrogen atom, X O, AO Ethyl epoxide, the compound that n2 is 60, as R21The HLB of-H compound is -1.55.〕
[table 9]
[table 10]
* 1 addition：Relative to the addition (mass parts) of the mass parts of cement 100
* 2-in-1 meter addition：Add relative to (A) composition of the mass parts of cement 100, (B) composition and the total of (C) composition Dosage (mass parts)
In comparative example 7-1,7-2, mortar flows are larger with the reduction of time, cannot get the sufficient up time.
In comparative example 7-3, the mortar flows after being kneaded 2.5 minutes are small, cannot get initial mobility.
In embodiment 7-1, mortar flows are small with the variation of time, cannot get the sufficient up time.

Claims (12)

1. a kind of dispersant for hydraulic composition composition, it contains：
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolysis be changed into phosphorus The monomeric unit of group in the group of acidic group and with the monomeric unit of alkylene oxide group, weight average molecular weight be 1,000 with It is upper and 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) More than a kind of compound in compound represented by represented compound and following formulas (C4),
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
In formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression more than 1 And less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be more than 1 and Less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.
2. dispersant for hydraulic composition composition according to claim 1, wherein, also contain (D) defoamer.
3. dispersant for hydraulic composition composition according to claim 1 or 2, wherein, (A) contracts for naphthalenesulfonateformaldehyde formaldehyde Compound or its salt.
4. according to dispersant for hydraulic composition composition according to any one of claims 1 to 3, wherein, (A) and (B) Mass ratio be calculated as more than 0.01 and less than 100 with (A)/(B).
5. a kind of hydraulic-composition, contains：
Hydraulic powder,
Water,
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolysis be changed into phosphorus The monomeric unit of group in the group of acidic group, with the monomeric unit of alkylene oxide group, weight average molecular weight be more than 1,000 And 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) More than a kind of compound in compound represented by represented compound and following formulas (C4),
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
In formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression more than 1 And less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be more than 1 and Less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.
6. hydraulic-composition according to claim 5, wherein, also contain (D) defoamer.
7. the hydraulic-composition according to claim 5 or 6, wherein, (A) is naphthalene sulfonic acid-formaldehyde condensation product or its salt.
8. the hydraulic-composition according to any one of claim 5~7, wherein, relative to the mass of hydraulic powder 100 Part, containing more than (A) 0.01 mass parts and below 2 mass parts.
9. the hydraulic-composition according to any one of claim 5~8, wherein, relative to the mass of hydraulic powder 100 Part, containing more than (B) 0.01 mass parts and below 2 mass parts.
10. the hydraulic-composition according to any one of claim 5~9, wherein, relative to the matter of hydraulic powder 100 Part is measured, containing more than (C) 0.01 mass parts and below 1.5 mass parts.
11. the hydraulic-composition according to any one of claim 5~10, wherein, (A) and (B) mass ratio with (A)/(B) is calculated as more than 0.01 and less than 100.
12. a kind of inorganic particle dispersant composition, it contains：
(A) there is the high-molecular compound for wrapping naphthalene-ring containing monomeric unit,
(B) contain with selected from carboxylic acid group, phosphate, by hydrolysis be changed into carboxylic acid group group and by hydrolysis be changed into phosphorus The monomeric unit of group in the group of acidic group, with the monomeric unit of alkylene oxide group, weight average molecular weight be more than 1,000 And 1, less than 000,000 polymer, and
(C) selected from the compound represented by following formulas (C1), the compound represented by following formulas (C2), following formulas (C3) More than a kind of compound in compound represented by represented compound and following formulas (C4),
R11-X-(AO)n1-SO3M (C1)
R21-X-(AO)n2-R22 (C2)
In formula,
R11Expression makes as R11The HLB of-H compound is less than 5.10 alkyl,
R21Expression makes as R21The HLB of-H compound is less than 5.10 alkyl,
R31Expression makes as R31The HLB of-H compound is less than 5.10 alkyl,
R41Expression makes as R41The HLB of-H compound is less than 5.10 alkyl,
R22、R32、R33It is identical or different, hydrogen atom or carbon number more than 1 and less than 3 alkyl are represented respectively,
Y1、Y2It is identical or different, respectively hydrogen atom or SO3M, Y1、Y2At least one be SO3M,
AO represents carbon number more than 2 and less than 4 alkylene oxide group,
n1For AO average addition molal quantity, more than 0 and less than 300 number is represented,
n2For AO average addition molal quantity, more than 1 and less than 300 number is represented,
n3、n4It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n3And n4Total expression more than 1 And less than 300 number,
n5、n6It is identical or different, respectively AO average addition molal quantity, be more than 0 number, n5And n6It is total be more than 1 and Less than 300 number, n5In the case of 0, Y1For hydrogen atom, n6In the case of 0, Y2It is hydrogen atom,
X represents O or COO,
M represents counter ion counterionsl gegenions.
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